Chemical Engineering Primer

with Computer Applications

Chemical Engineering Primer
with Computer Applications

Hussein K. Abdel-Aal
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Library of Congress Cataloging‑in‑Publication Data

Names: Abdel-Aal, Hussein K., author.

Title: Chemical engineering primer with computer applications / Hussein K.
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Description: Boca Raton : CRC Press, 2017. | Includes bibliographical
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Identifiers: LCCN 2016034556 | ISBN 9781498730570 (paperback : acid-free
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Contents
Preface.................................................................................................................... xiii
Acknowledgments ..................................................................................................xvii
Author .....................................................................................................................xix
Introduction: Initial Thoughts .................................................................................xxi

Section i An insight into chemical engineering

Chapter 1 Introductory Concepts ..........................................................................3

1.1 System of Units..........................................................................3
1.2 Process Variables.......................................................................6
1.2.1 Temperature Scales ......................................................6
1.2.2 Pressure Scale...............................................................7
1.3 Gas Laws ...................................................................................9
1.3.1 Boyle’s Law ..................................................................9
1.3.2 Charles’ Law ................................................................9
1.3.3 Dalton’s Law .................................................................9
1.3.4 Ideal Gas Law............................................................. 10
1.3.5 Raoult’s Law ............................................................... 12
1.3.6 Amagat’s Law............................................................. 13
1.3.7 Avogadro’s Hypothesis ............................................... 14
End-of-Chapter Solved Examples ...................................................... 14
References .......................................................................................... 18

Chapter 2 Basic Principles and Introduction to Calculations ............................. 19

2.1 The Two Building Blocks of Chemical Engineering: Unit
Operation and Unit Processes ................................................. 19
2.2 Chemical Process Industry ......................................................20
2.3 Chemical Plant ........................................................................ 21
2.4 Process Design ........................................................................ 22
2.5 Role of Material and Energy Balances,
Thermodynamics, and Kinetics .............................................. 22
2.6 Design Variables for Sizing Piping and Process Equipment ... 23
2.7 Basic Definitions......................................................................24
2.8 Conversion of Physical Events and Principles to
Mathematical Formula ............................................................24
2.9 Basic Laws ...............................................................................25
2.9.1 Mass and Energy Conservation: Material
Balance and Heat Balance..........................................25

v
vi Contents

2.9.2 Thermodynamics........................................................26
2.9.3 Some General Tips .....................................................26
2.9.3.1 Parts-Per Notation......................................26
2.9.3.2 Frequently Asked Questions ....................... 27
End-of-Chapter Solved Examples ...................................................... 27
Reference ............................................................................................ 32

Section ii Fundamentals and Problem-Solving
Profile

Chapter 3 Numerical Methods and Chemical Engineering Computations ........ 35

3.1 Introduction ............................................................................. 35
3.2 Basic Definitions and Introductory Remarks .......................... 36
3.2.1 Algorithms.................................................................. 36
3.2.2 Programming Language............................................. 36
3.3 Areas and Domain of Numerical Methods ............................. 36
3.4 Applications Using Elementary Numerical Methods.............. 37
End-of-Chapter Solved Examples ...................................................... 38
References .......................................................................................... 43

Chapter 4 The Approach to Solve Problems by Computers ............................... 45

4.1 Introduction ............................................................................. 45
4.2 Methodology ............................................................................46
4.3 Model Development and Mathematical Formulation .............. 47
4.4 Applications ............................................................................. 50
4.4.1 Problem Statement ..................................................... 50
End-of-Chapter Solved Examples ...................................................... 52
References .......................................................................................... 65

Section iii Backbone Materials

Chapter 5 Fluid Flow and Transport of Fluids.................................................... 69

5.1 Introduction ............................................................................. 69
5.2 Definitions and Terminology in Fluid Mechanics ................... 70
5.2.1 Compressible and Noncompressible Fluids................ 70
5.2.2 Pressure Concept ........................................................ 70
5.2.3 Forces Acting on a Fluid ............................................ 70
5.2.4 Nature of Fluids.......................................................... 71
Contents vii

5.3 Classification of Fluid Flow..................................................... 71

5.3.1 Ideal Fluid Flow ......................................................... 72
5.3.2 Real Fluid Flow .......................................................... 72
5.3.3 Steady and Unsteady State Flow ................................ 72
5.3.4 Uniform and Nonuniform Flow ................................. 72
5.3.5 Laminar Flow ............................................................. 72
5.3.6 Turbulent Flow ........................................................... 72
5.4 Parameters in Laminar Flow ................................................... 73
5.4.1 Velocity Gradient or Rate of Shear Stress (du/dy) ..... 73
5.4.2 Shear Stress (τ) ........................................................... 74
5.5 Fluid Statics ............................................................................. 74
5.5.1 Gauge Pressure and Absolute Pressure ...................... 74
5.6 Overall Energy Balance Equation ........................................... 75
5.6.1 Introduction ................................................................ 75
5.6.2 General Energy Balance Equation ............................. 75
5.6.3 Special Cases.............................................................. 76
5.6.4 Mechanical Energy Balance....................................... 76
5.6.5 Bernoulli’s Equation ................................................... 77
5.6.6 Head Form of Bernoulli’s Equation ........................... 78
5.6.7 Pressure Drop and Friction Losses ............................ 78
5.7 Piping and Pumps ....................................................................80
5.7.1 Introduction ................................................................80
5.7.2 Piping .........................................................................80
5.7.2.1 Sizing of Pipelines ......................................80
5.7.2.2 Economic Balance in Piping and
Optimum Pipe Diameter.............................80
5.7.2.3 Stepwise Procedure to Calculate the
Wall Thickness ........................................... 81
5.7.2.4 Relationship between the Pipe
Diameter and the Pressure Drops ............... 82
5.7.3 Pumps ......................................................................... 83
5.7.3.1 Introduction ................................................ 83
5.7.3.2 Classification and Types of Pumps .............84
5.7.3.3 How to Select a Pump? ............................... 85
5.7.3.4 Calculation of the Horsepower for
a Pump ...................................................... 86
End-of-Chapter Solved Examples ...................................................... 86
References ..........................................................................................94

Chapter 6 Heat Transmission .............................................................................. 95

6.1 Introduction ............................................................................. 95
6.2 Modes of Heat Transfer ...........................................................96
6.3 Heat Transfer by Conduction ...................................................97
viii Contents

6.3.1 Fourier’s Law..............................................................97

6.3.2 Thermal Conductivity ................................................ 98
6.3.3 Conduction through a Hollow Cylinder .....................99
6.3.4 Conduction through Solids in Series ..........................99
6.3.5 Solved Examples ........................................................99
6.4 Heat Transfer by Convection ................................................. 101
6.4.1 Introduction .............................................................. 101
6.4.2 Methodology of Calculation ..................................... 102
6.4.3 Convective Heat Transfer Coefficient ...................... 102
6.5 Overall Heat Transfer Coefficient ......................................... 103
6.5.1 Background .............................................................. 103
6.5.2 Discussion................................................................. 103
6.6 Heat Transfer by Radiation .................................................... 106
6.6.1 Introduction .............................................................. 106
6.6.2 Blackbody Radiation ................................................ 107
6.7 Heat Exchangers .................................................................... 107
6.7.1 Types of Heat Exchangers ........................................ 107
6.7.2 Log Mean Temperature Difference .......................... 108
6.7.3 Design of Heat Exchangers ...................................... 109
End-of-Chapter Solved Examples .................................................... 110
6A Appendix: Internal-Flow Convection Correlations ............... 116
Reference .......................................................................................... 117

Chapter 7 Two-Phase Gas–Liquid Diffusional Operations: Distillation

and Absorption ................................................................................. 119
7.1 Part I: Distillation .................................................................. 120
7.1.1 Introduction .............................................................. 120
7.1.1.1 Basic Concepts and Principles .................. 120
7.1.2 Three Pillars for Distillation .................................... 123
7.1.3 Features of Distillation Units ................................... 124
7.1.3.1 Types of Distillation Columns .................. 125
7.1.3.2 Overhead Condensers ............................... 125
7.1.3.3 Reflux and Reflux Ratio: Top of
Column ................................................. 126
7.1.3.4 Reboilers: Bottom of Column ................... 127
7.1.3.5 Rectification and Stripping Sections in
Distillation Columns ................................. 127
7.1.3.6 Effect of Operating Pressure .................... 127
7.1.4 Design of Distillation Columns ................................ 129
7.1.4.1 Introduction .............................................. 129
7.1.4.2 Approach to Solve Distillation
Problems ............................................... 130
7.1.4.3 Physical Models for Distillation ............... 131
7.1.4.4 Calculation of Number of Trays ............... 131
Contents ix

7.1.5 McCabe–Thiele Method ........................................... 132

7.1.5.1 Introduction .............................................. 132
7.1.5.2 Assumptions ............................................. 132
7.1.5.3 Procedure .................................................. 132
7.1.5.4 Illustration of How to Use Excel to
Solve a Problem ........................................ 134
7.1.5.5 Total and Minimum Reflux: Limiting
Cases ......................................................... 138
7.1.5.6 Tray Efficiency.......................................... 138
7.1.5.7 Stage Design and Efficiency ..................... 140
7.1.6 Shortcut Methods: Fenske–Underwood–Gilliland .... 142
7.1.6.1 Introduction .............................................. 142
7.1.6.2 Fenske Equation........................................ 142
7.1.6.3 Underwood Equation ................................ 142
7.1.6.4 Gilliland’s Method .................................... 143
7.1.7 Column Diameter ..................................................... 144
7.1.8 Flash Distillation ...................................................... 144
7.1.8.1 Flash Equation .......................................... 146
7.1.9 Reactive Distillation ................................................. 147
7.2 Part II: Absorption and Stripping .......................................... 147
7.2.1 Basic Concepts ......................................................... 148
7.2.2 Outline of Design Approach .................................... 149
7.2.3 Graphical Methods: Solution for Simple
Countercurrent Absorption Operations .................... 150
7.2.4 Material Balance Calculations ................................. 151
7.2.5 Analytical Methods: Equations to Calculate the
Number of Stages for Absorbers/Strippers .............. 154
7.2.6 Transfer Unit Concept for Absorption in Packed
Columns ................................................................... 156
7.2.7 Role of Absorption in Natural Gas Field
Processing ................................................................156
End-of-Chapter Solved Examples .................................................... 157
Reference .......................................................................................... 164

Chapter 8 Reaction Kinetics, Chemical Reactors, and Thermodynamics........ 165

8.1 Part I: Fundamentals of Reaction Kinetics ........................... 166
8.1.1 Introduction .............................................................. 166
8.1.2 Six Categories of Chemical Reactions ..................... 167
8.1.3 Reaction Rates .......................................................... 168
8.1.3.1 Forms of Rate Law ................................... 168
8.2 Part II: Types and Design of Chemical Reactors .................. 172
8.2.1 Introduction .............................................................. 172
8.2.2 Types of Laboratory and Industrial Catalytic
Reactors .................................................................... 173
x Contents

8.2.3 Catalytic Reactors .................................................... 174

8.2.4 Design of Chemical Reactors ................................... 175
8.2.4.1 Basic Design Equations ............................ 176
8.3 Part III: Introduction to Thermodynamics ............................ 178
8.3.1 Basic Definitions and Concepts................................ 178
8.3.1.1 The Concept of Equilibrium ..................... 178
8.3.1.2 The Concept of a Process ......................... 178
8.3.1.3 Equations of State ..................................... 178
8.3.2 Thermodynamic Laws and Entropy ......................... 179
8.3.2.1 Entropy ..................................................... 179
8.3.3 Role of ∆G in Chemical Reactions .......................... 180
End-of-Chapter Solved Examples .................................................... 181
Part (a): Manual Calculations ................................................ 181
Part (b): Using MATLAB® .................................................... 184
References ........................................................................................ 186

Chapter 9 Chemical Plant Design and Process Economics .............................. 187

9.1 Introduction ........................................................................... 188
9.2 Plant Design is the Heart of Chemical Engineering ............. 188
9.3 How to Handle a Design Project?.......................................... 189
9.3.1 Proposed Procedure ................................................. 189
9.3.2 A–Z Chart for Plant Design ..................................... 190
9.3.3 Flow Sheeting and Types of Flow Diagrams ........... 191
9.3.4 Scale-Up Practice and Safety Factors ...................... 191
9.4 Other Aspects in Plant Design .............................................. 191
9.5 The Role of Economics in Plant Design................................ 193
9.5.1 Introduction .............................................................. 193
9.5.2 Estimation of the Fixed Capital Investment and
the Total Capital Investment .................................... 193
9.5.3 Decision Making Use of Annuity ............................ 194
9.5.4 Profitability Analysis Using Economic Indicators....195
9.5.4.1 The Annual Rate of Return ...................... 195
9.5.4.2 Payout Period, Payback Time, or Cash
Recovery Period........................................ 196
9.5.4.3 Discounted Cash Flow Rate of Return
and Present Value Index ........................... 196
9.5.4.4 Net Present Value...................................... 196
End-of-Chapter Solved Examples .................................................... 196

Chapter 10 Case Studies ..................................................................................... 201

10.1 Introduction ........................................................................... 201
10.2 Case Study 1: Alternatives to Storage of Ammonia ..............202
10.2.1 Introduction ..............................................................202
10.2.2 The Problem .............................................................202
Contents xi

10.2.3 Approach ..................................................................202

10.2.4 Conclusions ..............................................................203
10.2.5 Discussions ...............................................................204
10.3 Case Study 2: Flash Dewatering of Raw Sewage Effluents .....204
10.3.1 Introduction ..............................................................204
10.3.2 The Problem .............................................................204
10.3.3 Proposed Scheme .....................................................204
10.3.4 Process Description ..................................................206
10.3.5 Conclusions ..............................................................207
10.3.6 Discussions ...............................................................208
10.4 Case Study 3: Magnesium Extraction from Seawater ...........208
10.4.1 Introduction ..............................................................208
10.4.2 Proposed Method .....................................................209
10.4.3 Production of Magnesium Metal from
Magnesium Chloride ................................................ 210
10.4.4 Discussions ............................................................... 210
10.5 Case Study 4: Chemical Desalting of Brines ........................ 210
10.5.1 Introduction .............................................................. 210
10.5.2 Methodology ............................................................ 210
10.5.3 Main Reactions......................................................... 211
10.5.3.1 Process Synthesis with Modifications ...... 212
10.5.3.2 Consumption–Production Analysis .......... 212
10.5.3.3 Comparison between the
Solvay Process and the Proposed
Process .................................................... 213
10.5.4 Conclusion ................................................................ 215
10.5.5 Discussion and Problem Formulation ...................... 215
10.6 Case Study 5: Applications of Differential Equations........... 216
10.6.1 Introduction .............................................................. 216
10.6.2 Problem Statement ................................................... 216
10.6.3 Proposed Approach .................................................. 216
10.6.4 Discussions ............................................................... 218
10.7 Case Study 6: Reactive Distillation ....................................... 218
10.7.1 Introduction .............................................................. 218
10.7.2 Objective................................................................... 218
10.7.3 Discussion................................................................. 219
References ........................................................................................ 219
Appendix A: Application Problems.................................................................... 221
Appendix B: Mathematical Methods and Review Notes .................................. 235
Appendix C: Conversion Tables ......................................................................... 243
Bibliography ......................................................................................................... 247
Index ...................................................................................................................... 251
Preface
It has been observed that most of the textbooks written for introductory courses in
chemical engineering follow a formal classical method. This applies, in particular,
to texts for sophomore courses. Authors normally focus on writing many chapters
on material balance and energy balance followed by those on allied topics. What we
have used here is a different approach to offer an introductory course in chemical
engineering, with emphasis on handling computer solutions for chemical engineer-
ing problems. Our aim is to introduce the reader to chemical engineering funda-
mentals without the distractions, which is the case with the material found in many
textbooks.
This book has been written as a beginning chemical engineering text with empha-
sis on computer applications. The word beginning is the underlying paradigm of
writing this book. It is the act or process of bringing this knowledge to young stu-
dents majoring in chemical engineering at different levels. The meaning may also
infer the beginning to walk into the real world right after finishing the bachelor’s
degree. In this way, this book should be of use to both chemical engineering students
as a point of departure for their entry into industry and the practicing engineer for
their continuing education program.
For a practicing chemical engineer, whether in industry or teaching, this book
would be a good companion that adequately treats chemical engineering as a com-
posite and integrated field.
This book covers the core concepts of chemical engineering, ranging from conser-
vation laws all the way up to chemical kinetics. For nonengineers, who are expected
to work with chemical engineers on projects, scale-ups, and process evaluations, this
primer would be an excellent source for a solid understanding of basic concepts of
chemical engineering analysis, design, and calculations.
The text is divided into three sections.

SECTION I: INSIGHT INTO CHEMICAL

ENGINEERING—CHAPTERS 1 AND 2
Chapter 1, “Introductory Concepts,” introduces the essentials of chemical engi-
neering along with unit system. Chapter 2, “Basic Principles and Introduction to
Calculations,” reviews well-known physical and chemical laws in continuation
to Chapter 1. In addition, the principles underlying chemical engineering problems
are presented.

SECTION II: FUNDAMENTALS AND PROBLEM-SOLVING

PROFILE—CHAPTERS 3 AND 4
This section deals with the methodology of how to devise and evaluate numerical
techniques for employing computers, through standard algorithm, in order to solve
chemical engineering problems. The focus of numerical methods as presented is to

xiii
xiv Preface

translate chemical engineering problems into algorithms and implement them in a

spreadsheet or programming language (e.g., MATLAB®).
Chapter 3, “Numerical Methods and Chemical Engineering Computations,”
is devoted to introducing numerical methods with emphasis on elementary ones.
Chapter 4, “The Approach to Solve Problems by Computers,” illustrates how to
tackle a solution of a problem by model building.

SECTION III: BACKBONE MATERIALS OF CHEMICAL

ENGINEERING—CHAPTERS 5 THROUGH 10
Section III extensively covers the basic principles underlying chemical engineer-
ing in all major processes, focusing on their scientific realization and applications.
Solving problems arising in fluid mechanics, distillation, chemical reaction engi-
neering, and others is heavily emphasized in this section. The contents of the chap-
ters are as follows:

• Chapter 5—“Fluid Flow and Transport of Fluids”

• Chapter 6—“Heat Transmission”
• Chapter 7—“Two-Phase Diffusional Operations: Distillation and Absorption”
• Chapter 8—“Reaction Kinetics, Reactor Design, and Thermodynamics”
• Chapter 9—“Process Economics and Chemical Plant Design”
• Chapter 10—“Case Studies”

The material in each chapter in Section III, excluding Chapter 10, encompasses two
sections: one covers the theoretical principles in a condensed format, and the other
presents a set of numerically solved problems using interactive numerical software
packages.
Chapter 10, on the other hand, introduces a number of case studies that handle
practical technical problems. Many of these case studies are compiled by the author
in the field of applied research, in both academy and industry.
This primer in chemical engineering would serve as a text for students majoring
in chemical engineering, applied chemistry, and biochemical process engineering.
This book is designed to be used by students in a variety of ways, dependent on
the level of enrollment. Possible recommendations are as follows:

• Level one, sophomore students studying a course on the basic principles

in chemical engineering with programming and computer applications:
Chapters 1 through 4.
• Level two, junior students seeking courses on numerical solution of chemi-
cal engineering problems or/and unit operations on fluid flow and heat
transfer: Chapters 1 through 6.
• Level three, senior students: The text in Chapters 7 through 9 is recom-
mended for a course as a continuation for unit operations to cover distilla-
tion and absorption. Kinetics and reactor design and plant design are other
topics to be considered for additional course(s).
Preface xv

This book takes a highly pragmatic approach to presenting the principles and appli-
cations of chemical engineering and offering a valuable, easily accessible guide to
solve problems using computers. MATLAB and spreadsheeting are applied in solv-
ing many examples.
Problems assigned for each chapter and found in Appendix A, ranging from simple
to difficult, allow readers to gradually build their skills and be able to tackle a broad
range of problems in chemical engineering. In addition, the numerous real examples
throughout this book (more than 70) include computer or hand solutions, or in many
cases both. Many solved example problems reinforce the concepts covered. The text is
written with a view that solving problems is an essential part of the learning process.
It gives a taste of the kinds of problems with which chemical engineers grapple. It puts
a wealth of solved practical problems at your fingertips.
One of the main unique features of this book is that it is a convenient source in
chemical engineering that can be used at ease, without the need for many compre-
hensive texts. It is an integrated form of a single source.
In conclusion, one can say that two things are important: “Science…means un-
resting endeavor and continually progressing development toward an aim which the
poetic intuition may apprehend, but the intellect can never fully grasp.” Chemical
engineering is the discipline that uses a molecular understanding of matter to
produce—from raw materials—all the synthetic materials humankind is using.

MATLAB® is a registered trademark of The MathWorks, Inc. For product informa-

tion, please contact:

The MathWorks, Inc.

3 Apple Hill Drive
Natick, MA 01760-2098 USA
Tel: 508-647-7000
Fax: 508-647-7001
E-mail: [email protected]
Web: www.mathworks.com
Acknowledgments
When authors like me get involved in writing a book, they are rather being optimistic.
Optimism is the essential ingredient for success. Getting help and support from
many individuals provides inspiration that fuels the author’s journey through the
writing process.
In this respect, I gratefully acknowledge my indebtedness to a number of col-
leagues who enriched this book by their valuable contributions, either in review-
ing and shaping some chapters or providing sets of solved examples and problems.
Helpful suggestions offered by many of them are acknowledged. On the top of the
list are Dr. Adnan Zahed (KAU, Jeddah, Saudi Arabia), for his contribution to writ-
ing Chapter 6; Dr. Mazen Al-Shalbi (KFUPM, Dhahran, Saudi Arabia), for his con-
tribution to writing Chapter 8; and Dr. Maha Abdel-Kereem and Dr. Khaled Zohdi
(both with HTI, Tenth of Ramadan, and Egypt).
In addition, help and good support were received—at an early stage of writing—
from a number of colleagues: Dr. Mohamed Basyouni and Dr. Sherene Abdelhamid
(both with HTI), Dr. Mohmed Helmy and Asmaa Harraz (both with Alexandria
University), and Eman Abdel-Aal (Dubai Women’s College).
I am especially indebted to a group of my students, at KFUPM and HTI, for
including some of their homework-solved-problems in the text.
Last but not least, a word of appreciation to the staff at Taylor & Francis Group
for their cooperative support and dedication in getting this book in the hands of the
readers. This includes Allison Shatkin, Kari Budyk, and Robert Sims.

xvii
Author
Professor Hussein K. Abdel-Aal is emeritus professor of chemical engineering and
petroleum refining, NRC, Cairo, Egypt. He received his BS in chemical engineering
in 1956 from Alexandria University and MS and PhD in chemical engineering in
1962 and 1965, respectively, from Texas A&M University, College Station, Texas.
Professor Abdel-Aal joined the Department of Chemical Engineering at
KFUPM, Dhahran, Saudi Arabia (1971–1985). He was the head of department for
the period 1972–1974. He was also visiting professor with the Chemical Engineering
Department at Texas A&M (1980–1981). In 1985–1988, he assumed the responsi-
bility of the head of the Solar Energy Department, NRC, Cairo, before rejoining
KFUPM for the period 1988–1998.
Professor Abdel-Aal conducted and coordinated projects involving a wide range
of process development, feasibility studies, industrial research problems, and con-
tinuing education programs for many organizations, including Suez Oil Processing
Company, Petromin in Riyadh (Saudi Arabia), Arab Petroleum Investment Corp in
Dhahran (Saudi Arabia), Hagler-Baily & Company, Washington DC, Mobil/Esso Oil
Companies in Libya, and Kuwait oil companies.
Professor Abdel-Aal has contributed to more than 90 technical papers, is the edi-
tor of Petroleum Economics & Engineering, third edition (2014), and is the main
author of the textbook Petroleum and Gas Field Processing, second edition, (2016).
Both books were published by Taylor & Francis Group/CRC Press.
Professor Abdel-Aal is listed in Who’s Who in the World (1982) and is a member
of AICHE, Sigma Si, Phi Lambda Upsilon. He is a fellow and founding member of
the board of directors of the International Association of Hydrogen Energy.

xix
Introduction: Initial Thoughts
I.1 OBJECTIVES
For a student, taking the first course in their major is an exciting but scary step
into the unknown. Effectively introducing chemical engineering education to under-
graduate students is usually difficult, especially when teaching introductory courses.
A prime pitfall of the larger texts is that students are disinclined to read several pages
of text to solve a problem.
Experience in teaching the first course has shown that there is a need for such a
handy, collective, and summarized source of basic principles in chemical engineer-
ing, especially when solving problems. The methodology of solving problems and
their solutions should be presented hand in hand with the fundamentals, as discussed
in this text.
This primer is to be considered a survival companion for students of chemical
engineering. As you navigate through the text, you can maneuver smoothly from
chapter to chapter. The two main themes embodied in this text are as follows:

• Theme No. 1: To provide students with some guide steps on how to identify
the type of problems to solve and how to target a solution. Focus will be on
the use of systematic algorithms that employ numerical methods to solve
different chemical engineering problems by describing and transforming
the information.
• Theme No. 2: To present the basic principles and techniques in chemical
engineering and the underlying unit operations and chemical processes in a
concise and nontraditional format with numerous applications.

Let us first acquaint our readers with the field of chemical engineering. All engi-
neers employ mathematics, physics, and the engineering art to overcome technical
problems safely and economically. Yet it is the chemical engineer alone that draws
upon the vast and powerful science of chemistry to solve a wide range of problems.
Chemical engineers use chemistry and engineering to turn raw materials into usable
products, such as petrochemicals, plastics, and pharmaceutical ingredients. They
apply physical science together with mathematics and computers to processes that
involve physical changes and/or chemical reactions in order to produce more valu-
able products.
Every scientific discipline, including chemical engineering, relies on the use of
computers and software. The capabilities provided by computers, such as fast cal-
culations, large storage capacity, and software, permit engineers to solve different
problems.

xxi
xxii Introduction: Initial Thoughts

Therefore, scientists depend on computational methodology in solving their prob-

lems. It is based on the following fact:

Computational science is a function of two components: theoretical and practical one.

The theoretical component involves the use of systematic algorithms to solve dif-
ferent scientific problems by describing and transforming the information, while the
practical component involves the implementation of the computational hardware
and software.
Traditionally, in solving scientific problems, researchers use either of the following:

• Theoretical approach
• Laboratory experiment

In the theoretical approach, scientists rely upon the use of some classified models,
in accordance with how they are derived. In general, three models are well known:

1. Theoretical models (transparent models): These are developed using the

principles of chemistry and physics.
2. Empirical models (black box models): These are obtained from a math-
ematical or statistical process of operating data—process identification.
3. Semiempirical models (gray box models): These models represent a com-
promise between (1) and (2), with one or more parameters to be evaluated
from plant data.

Computational science, on the other hand, is different from these two traditional
approaches, the theoretical and the practical, as illustrated in Figure I.1. The scientific

Architecture
(computing environment)
n
tio

Ex
uta

pe
ri
mp

me
Co

Model
nt

Theory

Application Algorithm
(science) (mathematical model)

FIGURE I.1 Model of relationship among theory, computation, and experiment.

Introduction: Initial Thoughts xxiii

computing avenue is to gain understanding, mainly through the analysis of math-

ematical models implemented on computers.
Computers play a vital role in almost every aspect of modern chemical engineer-
ing, which may include the following applications:

1. Supercomputers to simulate complex chemical processes and plant

operations
2. Computational fluid dynamics to simulate flow systems and heat transfer
problems
3. MATLAB®, polymath, spreadsheeting, and others to solve many problems
including differential equations
4. Aspen computer technology to simulate unit operations and processes

I.2 PROPOSED APPROACH

It was observed that frequently students had to supplement their technical knowl-
edge when solving a problem. For example, in solving problems on flash distilla-
tion, a refresher to some basic concepts is necessary. Definitions of bubble point,
dew point, and derivation of the flash equation are needed in problem solving.
This book, a self-contained source on chemical engineering, will come in handy
in such situations.
As an instructor in your first course, an attractive way to introduce your students
to the field of chemical engineering is to present to them the following simple illus-
trative example of a petroleum fractionation process.

I.2.1 IllustratIve example of petroleum fractIonatIon process

Crude oil is to be fractionated into straight-run products such as gasoline and gas oil.
It is heated first by heat exchangers and then desalted. Its temperature is raised next
using fire heaters, before it is introduced to the fractionation tower. This process is
illustrated in Figure I.2.
The next step is to explain to them how and why the crude oil is separated into
products.
Well, in the transformation of raw materials (crude oil) and in the presence of
energy (heat) to produce finished products, three modes of transfer are encountered.
Now, it may prove beneficial to examine in some detail the transport phenomena
involved. They are known as

1. Momentum transfer (fluid flow), using a pump

2. Heat transfer of oil, using heat exchangers and a furnace
3. Mass transfer in the distillation column that leads to the separation of crude
oil into different cuts (transfer is due to the molecular diffusion of compo-
nents that separates the light from heavy)

The physical operations (known as unit operations and shown in the earlier exam-
ple) are fluid flow, heat transfer, and distillation. They are basically based on these
xxiv Introduction: Initial Thoughts

Crude oil Air-cooled

condenser Gas
Pump

Crude
2 atm 43°C Reflux
oil Reflux
drum

Hot products or pumparound Sour

water
Pump
Mixing Crude oil
valve distillation Naphtha
Water
Desalter tower Crude oil
Crude Steam
Brine oil Kero
(jet fuel)
Pump Crude oil
or pumparound
Hot products

Pumparound Steam Light

gas oil
398°C Pump
Crude oil
Steam
Heavy
Crude oil gas oil
Fired Steam
Sidecut
heater Pump
strippers Crude oil

When the heat exchanger Residue

symbol is grayed like this, (fuel oil)
it is part of the crude oil Pump
preheat exchangers.

FIGURE I.2 Flow diagram for crude oil distillation.

modes of transfer. Unit operations deal chiefly with the transfer of energy and the
transfer, separation, and conditioning of materials by physical means.
At this stage, two basic questions arise:

1. What is the mechanism(s) underlying this process?

2. How and where does it take place?

The answer to the first question deals with theory of transfer or transport, as explained,
within the boundaries of our system. In answer to the second question, the combined
effect of momentum, heat, and mass (MHM) is responsible for the physical changes
that take place in the distillation column to produce the finished products.
Further, assume that the gasoline exiting the distillation column is introduced into
what is known as a reforming unit in order to obtain a higher-grade gasoline. This
reforming process represents a typical example of a chemical conversion or chemi-
cal reaction—known as unit process—where hydrocarbons undergo molecular
changes and rearrangement leading to high-octane gasoline. Unit processes involve
primarily the conversion of materials by means of chemical reactions. Again, it
should be pointed out that the three modes of transfer, MHM, take place for opera-
tions involving chemical reactions, or chemical changes, as well.
Introduction: Initial Thoughts xxv

Now, having presented this example, one should elaborate the concepts of unit
operations, unit processes, and transport phenomena. This will pave the way to the
students when they come to the heart of the materials embodied in the text.

I.3 ROLE OF UNIT OPERATIONS, UNIT PROCESSES,

AND TRANSPORT PHENOMENA
I.3.1 Background
In early days, chemical engineering started as an applied or industrial chemistry.
As such, it was based on the study of definitive processes. Hence, the unit process
approach was used. Later on, it became apparent to the pioneers that certain aspects
in the industrial processes were common, such as fluid flow, heat transfer, mixing,
and separation technology.
This new perception led to the development and the creation of the new approach
of unit operations, replacing the unit process–based curriculum.
Although the unit operations were based on first principles, they represented a
semiempirical approach to the subject areas covered.
Later, a series of events resulted in another revolutionary response: the con-
cept of transport phenomena. The subject of transport phenomena includes three
closely related topics: fluid dynamics, heat transfer, and mass transfer. Fluid
dynamics involves the transport of momentum, heat transfer deals with the trans-
port of energy, and mass transfer is concerned with the transport of mass of vari-
ous chemical species. These modes of transfer frequently occur simultaneously in
industrial applications like distillation. The basic equations that describe the three
modes of transport phenomena are also closely related and can often be analyzed
by analogy. This is what is known as the engineering science approach to chemi-
cal engineering. The focal point of this approach is the rigorous mathematical
description of all physical rate processes of mass, heat, or momentum crossing
phase boundaries.
It was felt that this very last concept set the chemical engineering profession back
a few decades. Graduating chemical engineers were considered to be more applied
physicists than traditional chemical engineers, in terms of training.
Later, there was a return to the traditional approach in chemical engineering,
primarily as a result of the Accreditation Board for Engineering and Technology.

I.3.2 analysIs and dIscussIon

A unit operation, as explained before, deals chiefly with the transfer of energy and
the transfer, separation, and conditioning of materials by physical means. It repre-
sents a structure of logic used in the synthesis and analysis of processing schemes in
the chemical engineering field (chemical and process industries). The basic underly-
ing concept in these processes is as follows:

All processing schemes can be composed from and decomposed into a series of indi-
vidual or unit steps.
xxvi Introduction: Initial Thoughts

The following classification is normally adopted:

1. If a unit step involves a physical change, it is called unit operation.

2. If a unit step involves a chemical change, it is called unit process.

These unit operations cut across widely different processing applications, including
the manufacture of chemicals, fuels, pharmaceuticals, pulp and paper, and processed
foods. The unit operation approach serves as a very powerful form of morphological
analysis, which systematizes process design and greatly reduces both the number of
concepts that must be taught and the number of possibilities that should be consid-
ered in synthesizing a particular process, especially in plant design.
Most unit operations are based mechanistically upon the fundamental transport
processes of mass transfer, heat transfer, and fluid flow (momentum transfer), as
shown in the following table:

Type of Transport Process Unit Operations Based Upon

Mass transfer Distillation, solvent extraction, leaching, absorption/desorption,
adsorption, and others
Heat transfer Heat exchange, condensation, evaporation, furnaces or kilns,
drying, cooling towers, and others
Momentum transfer (fluid flow) Fluid transport (such as pumping), mixing/ agitation, filtration,
clarification, thickening, or sedimentation

It is important to point out that the study of transport phenomena provides a unifying
and powerful basis to understand different unit operations. The subject of transport
phenomena includes three closely related topics as shown earlier; of interest is mass
transfer, which is concerned with the transport of mass of various chemical spe-
cies. They frequently occur simultaneously in industrial applications like distilla-
tion, where the transport of mass occurs by diffusion for various chemical species.
The basic equations that describe the three modes of transport phenomena are also
closely related and can often be analyzed by analogy:

Transported Quantity Physical Phenomenon Equation

Momentum Viscosity ¶ru
t = -n
(Newtonian fluid) ¶x
Energy Heat conduction q dT
= -k
(Fourier’s law) A dx
Mass Molecular diffusion ¶C
J = -D
(Fick’s law) ¶x

The equation for momentum transport is Newton’s law of viscosity

¶rux
tzx = - n
¶z
Introduction: Initial Thoughts xxvii

where
τzx is the flux of x-directed momentum in the z direction
ν is μ/ρ, the momentum diffusivity
z is the distance of transport or diffusion
ρ is the density
μ is the viscosity

Newton’s law is the simplest relationship between the flux of momentum and the
velocity gradient.
The net flux of energy through a system, on the other hand, equals the conductiv-
ity, k times the rate of change of temperature with respect to position dT/dx.
where A is the surface area and q is the heat flow per unit time.
Finally, for mass transfer, the diffusion flux, J, from a higher concentration to a
lower concentration is proportional to the gradient of the concentration, dc/dx, of the
substance and the diffusivity, D, of the substance in the medium.
Based on this presentation, the following conclusions are drawn:

1. Chemical engineering is best defined as “the profession concerned with

the creative application of scientific principles underlying the transport of
mass, energy and momentum and the physical and chemical changes of
matter.” (American Institute of Chemical Engineers, 2003)
2. An economical method of organizing much of the subject matter of chemi-
cal engineering is based on using the concept of unit operation, as explained
earlier. This is basically justified for two reasons:
a. Many chemical processes can be broken down into a series of steps or
operations (units), which are repeated in other processes.
b. These individual steps or operations are based on the same scientific
principles and guidelines.

However, it is believed that there is no real conflict between the two approaches: the
unit operations and the transport phenomena. Most important is the development of
the skills that lead to the creative engineering use of the fundamentals or a combina-
tion of both, as demonstrated and presented in our book.

REFERENCE
American Institute of Chemical Engineers. AIChE Constitution. http://www.aiche.org/About/
WhoWeAre/Governance/Constitution.aspx, 2003. Retrieved August 13, 2011.
Section I
An Insight into Chemical
Engineering
Much of the background needed for an understanding of the materials embodied in
the text is basic science and engineering. To analyze and follow-up quantitatively
and to optimize the underlying processes in chemical engineering a profound knowl-
edge of theoretical background is needed. Section I, consisting of Chapters 1 and 2,
highlights a technical introduction to the basic principles and calculation techniques
introduced in the text.
Solved examples given in the chapters are straight forward direct applications.
They are hand-solved. It is meant to be a kind of refresher for a first course in chemi-
cal engineering curriculum. Some are worked out by Excel. Application problems
for Section I are included in Appendix A.
 1 Introductory Concepts

As indicated by the title of this chapter, the essentials of some chemical engineering
aspects are introduced. Most of the common systems of units used in calculations are
presented first. Temperature (T) and pressure (P) scales are discussed in detail next,
since both T and P are key process variables. For example, to design a distillation
column, information is needed about the boiling temperatures of the components
that should be separated. Physical gas laws that are frequently used in the calcula-
tions are described as well.

1.1 SYSTEM OF UNITS*

Our basic concepts of measurements are the following:

• Length L
• Time θ
• Mass M
• Temperature T

To express any physical property, you need two items: a value and a unit. For exam-
ple, we say the room temperature is 25°C. Another example is the dimensions of a
distillation column: 30 ft in length and 4.5 ft in diameter.
The most common systems of units are as given next:

Length Mass Time Energy

cgs cm g s J or cal
fps ft pound (lb) s ft · pdl
SIa m kg s Joule
Am · Engb ft lb · mass s or h Btu or hp · h

a SI, System International.

b Am · Eng, American Engineering.

In addition, we have what we call derived units, for example, velocity = ft/s = L/θ.
The International System of Units (abbreviated SI from the French Le Système inter-
national d’unités) is the modern form of the metric system. The standards, published
in 1960, are based on the meter–kilogram–second system rather than the centimeter–
gram–second (cgs) system, which, in turn, had several variants. It comprises a coherent
system of units of measurement built around seven base units, as shown in Figure 1.1.
The system has been nearly globally adopted. In the United States, metric units
are not commonly used outside of science, medicine, and the government. However,

* This section is modified after International Bureau of Weights and Measures (n.d.; 2016).

3
4 Chemical Engineering Primer with Computer Applications

A s

mole m

cd kg

FIGURE 1.1 The seven base units of International System of Units: Kelvin (temperature),
second (time), meter (length), kilogram (mass), candela (luminous intensity), mole (amount
of substance), and ampere (electric current). (With kind permission from Springer: Units
of Measurement: Past, Present and Future, International System of Units, 2009, 16,
Gupta, S.V.)

U.S. customary units are officially defined in terms of SI units. The United Kingdom
has officially adopted a partial metrication policy, with no intention of replacing
imperial units entirely.
The basic laws that we use can be easily memorized using the following math-
ematical relationships:

1. Mass × velocity ⇒ momentum ⇒ kg · m/s

2. Rate of change of momentum Þ d/dq ëémomentum ùû Þ d/dq[(mass) × (velocity)]
Þ (mass) × (acceleration) Þ kg × m/s2 Þ force Þ N

Newton
N

3. Force × distance ⇒ work, energy, quantity of heat ⇒ kg · m2/s2 ⇒ N · m

Joule
J

4. Rate of change of energy ⇒ d/dθ [kg · m2/s2] ⇒ kg · m2/s3 ⇒ power ⇒ J/s

Watt
W
Introductory Concepts 5

It is worth mentioning that many of the derived units in the SI system are given
special names with corresponding symbols. For example, force, which has the units
kg · m/s2, has been named Newton and given the symbol N. Similarly, energy is
defined as Newton ∗ meter or N · m, having the units m2 · kg/s2. Hence, it is named
Joule and given the symbol J, and the corresponding unit of power is joule per sec-
ond named Watt.
Now, let us examine the systems of units when it comes to using the conversion
factor, known as gc. Basically, we start with the Newton’s law:

F = C×m ×a (1.1)

where
F is the force
m is the mass
a is the acceleration
C is a constant, whose numerical value and units depend on those selected for the
units F, m, and a

• The cgs system: The unit of force is dyne where 1 g is accelerated at 1 cm/s2.
Equation 1.1 is rewritten as

F = [C](1 g)(1 cm/s2 ) Þ dyne (1.2)

Therefore, selecting C = 1 dyne/(g)(cm)/s2 and substituting this in Equation

1.2 results in F = 1 dyne.
• The SI system: The unit of force is Newton (N), where 1 kg is accelerated at
1 m/s2. Equation 1.1 is rewritten as

F = [C](1 kg)(1 m/s2 ) = N (1.3)

Therefore, selecting C = 1 N/(kg)(m)/s2 and substituting this in Equation 1.3

results in F = 1 N.
• The American engineering system: The unit force is 1  lbf, where 1 lbm is
accelerated at g ft/s2, where g is the acceleration of gravity. Equation 1.1
is rewritten as

F = [C](1 lb m )(g ft/s2 ) = 1 lbf (1.4)

For Equation 1.4 to hold, the units of C have to be C ⇒ (lbf )/[(lbm)(ft/s2)].

A numerical value 1/32.174 has been chosen for the constant. The inverse of C
has been given the special symbol gc:

gc = 32.174 [(ft )(lbm )] / [(s2 )(lbf )] (1.5)

6 Chemical Engineering Primer with Computer Applications

1.2 PROCESS VARIABLES

Process variable is a dynamic feature of a given process. Accurate measurement
of process variables is important all the way through the chemical process indus-
try. There are four commonly measured variables that affect the performance of a
process:

1. Temperature
2. Pressure
3. Flow
4. Level

We will limit our talk to the first two process variable, T and P.

1.2.1 temperature scales

There are three temperature scales in use today (BIPM, n.d.; International Bureau
of Weights and Measures, n.d., 2016):

1. Fahrenheit
2. Celsius
3. Kelvin

Fahrenheit temperature scale is a scale based on 32 for the freezing point of water
and 212 for the boiling point of water, the interval between the two being divided
into 180 parts.
Celsius temperature scale, also called centigrade temperature scale, is the scale
based on 0 for the freezing point of water and 100 for the boiling point of water. The
following formula can be used to convert a temperature from its representation on
the Fahrenheit (F) scale to the Celsius (C) value: C = 5/9(F − 32). The scale is illus-
trated in Figure 1.2.
Kelvin temperature scale is the base unit of thermodynamic temperature mea-
surement in the SI of measurement. Such a scale has as its zero point (absolute zero),
the theoretical temperature at which the molecules of a substance have the lowest
energy, as shown in Figure 1.3. Many physical laws and formulas can be expressed
more simply when an absolute temperature scale is used; accordingly, the Kelvin
scale has been adopted as the international standard for scientific temperature mea-
surement. The Kelvin scale is related to the Celsius scale. The difference between
the freezing and boiling points of water is 100° in each so that the Kelvin has the
same magnitude as the degree Celsius.
The following equation is used for temperature intervals rather than specific tem-
peratures: 1 K = 1°C = 9/5°F = 9/5°R.
Introductory Concepts 7

Water
212°F 100°C
boils

50°C
98.6°F 37°C
Water
32°F 0°C
freezes
–40°F –40°C
–50°C
Dry ice
–108°F –78°C
(solid CO2)
–100°C

–150°C
Liquid –191°C
–312°F air –200°C

–250°C
Absolute –273°C
–459°F
zero

Fahrenheit Celsius
(centigrade)

FIGURE 1.2 Temperature-scale relationship for Fahrenheit and Celsius.

1.2.2 pressure scale

Pascal (N/m 2) is the unit of pressure. Pressure is usually expressed with reference to
either absolute zero pressure (a complete vacuum) or local atmospheric pressure. As
shown in Figure 1.4, the following definitions apply:
• A perfect vacuum would correspond to absolute zero pressure.
• All values of absolute pressure are positive.
• Gauge pressures are positive if they are above atmospheric pressure.
• Gauge pressures are negative if they are below atmospheric pressure.

Pabs = Patm + Pgau (1.6)

As expressed in various units, the standard atmosphere is equal to the following:

• 1.0 atm
• 14.7 psia
• 760 mm Hg
• 29.92 in. Hg
• 33.91 ft water
• 100 × 103 Pa (pascals) or N (Newton) per sq. meter (N/m2) = 100 kPa
8 Chemical Engineering Primer with Computer Applications

400 K
Water
100°C 373 K
boils
350 K
50°C
300 K
0°C Water 273 K
freezes
250 K
–40°C
–50°C
Dry ice 200 K
–78°C
(solid CO2) 195 K
–100°C
150 K
–150°C
–191°C 100 K
–200°C Liquid 82 K
air
50 K
–250°C
Absolute
–273°C 0K
zero

Celsius Kelvin
(centigrade) (absolute)

FIGURE 1.3 Temperature-scale relationship for Celsius and Kelvin.

Gauge pressure

Absolute Vacuum pressure

pressure

Local
atmospheric Absolute pressure
pressure

Absolute zero
(complete vacuum)

FIGURE 1.4 Illustrations of pressure relationships.

Introductory Concepts 9

If pressure is measured by means of height of the column of liquid, other than mer-
cury, the following equation is used to relate height to pressure:

Pa = Pb + rgh

where
Pa is the pressure at the bottom of the column
Pb is the pressure at the top of the column
ρgh are the density of fluid, acceleration of gravity, and height of fluid column,
respectively

1.3 GAS LAWS

1.3.1 Boyle’s law
In a mathematical equation, Boyle’s law is expressed as P1V1 = P2V2 = PV = K.
Hence, V = K/P.
This equation states that the volume of a given mass of gas is inversely pro-
portional to its pressure, if the temperature remains constant. In other words,
if a container, with a fixed number of molecules inside, is reduced in volume,
more molecules will hit the sides of the container per unit time, causing a greater
pressure.

1.3.2 charles’ law

For an ideal gas at constant pressure, the volume is directly proportional to its
temperature:

V1 T1
= (1.7)
V2 T2

1.3.3 dalton’s law

Mathematically, the pressure of a mixture of gases can be defined as the summation

PT = Sp i = p1 + p2 + p3 +  + p n (1.8)

where pi represents the partial pressure of each component.

A partial pressure is defined as the pressure that would be obtained if the same
mass of individual gas was alone at the same VT and at the same temperature.
Since the number of moles of a component is proportional to its partial pressure,
the mole fraction of a component, A, is given by

pA pA
XA = = (1.9)
PT Sp i
10 Chemical Engineering Primer with Computer Applications

The most useful form in which the laws of a mixture of ideal gases can be put is as
follows:

Volume% = Pressure% = Mole%

1.3.4 Ideal gas law

From the statements given by Boyle and Charles, the following relationship is
developed:

PV = nRT (1.10)

where
R is the gas constant
n is the number of moles
T is the temperature
P is the pressure; both are in absolute units

In SI units, P is measured in pascals, V is measured in cubic meters, n is measured in

moles, and T is measured in Kelvin (the Kelvin scale is a shifted Celsius scale, where
0.00 K = −273.15°C, the lowest possible temperature).
The gas constant (also known as the molar, universal, or ideal gas constant,
denoted by the symbol R) is a physical constant that is featured in many fundamental
equations in the physical sciences, such as the ideal gas law and the Nernst equation.
The dimensions of R are recognized through the following analysis:

PV
R=
nT

where
P is the pressure
V is the volume
n is the chemical amount
T is the temperature

As pressure is defined as force per unit area, the gas equation can also be written as

Force/Area × Volume
R=
Amount × Temperature

Area and volume are (length)2 and (length)3, respectively. Therefore,

Force/(Length)2 ´ (Length)3
R=
Amount ´ Temperature
Introductory Concepts 11

Since

Force ´ Length = Work

Work
R=
Amount ´ Temperature

The physical significance of R is work per degree per mole. It may be expressed in
any set of units representing work or energy (such as joules), other units representing
degrees of temperature (such as degrees Celsius or Fahrenheit), and any system of
units designating a mole or a similar pure number that allows an equation of mac-
roscopic mass and fundamental particle numbers in a system, such as an ideal gas.
Values of R are found in Appendix B.
How much gas is present could be specified by giving the mass instead of the
chemical amount of gas. Therefore, an alternative form of the ideal gas law may
be useful. The chemical amount (n) (in moles) is equal to the mass (m) (in grams)
divided by the molar mass (M) (in grams per mole):

m
n=
M

By replacing n with m/M and subsequently introducing the density ρ = m/V, we get

m
PV = RT
M

R
P=r T
M

The ideal gas law is the equation of state of a hypothetical ideal gas. It is a good
approximation to the behavior of many gases under many conditions, although it has
several limitations, as shown in Figure 1.5.
Nevertheless, this form of the ideal gas law is very useful because it links pres-
sure, density, and temperature in a unique formula independent of the quantity of
the considered gas. The behavior of real gases usually agrees with the predictions
of the ideal gas equation to within ±5% at normal temperatures and pressures. At
low temperatures or high pressures, real gases deviate significantly from ideal gas
behavior.
One of the most useful equations to predict the behavior of real gases was devel-
oped by Johannes van der Waals (1837–1923). The complete van der Waals equation
is therefore written as follows:

ìï é n 2a ù üï
íP + ê 2 ú ý{V - nb} = nRT (1.11)
îï ë V û þï
12 Chemical Engineering Primer with Computer Applications

Departure from ideal gas behavior

8.4 H2
Ideal gas
R = 8.3145 8.3
N2
8.2
(J/mole K)
CO
8.1
8.0 O2
PV
nT

7.9
0 5 10 15 20
P (atm)

FIGURE 1.5 Deviations of gases from the ideal gas law.

From the definition of partial pressure as given before, one can say for a number of
components of a gas mixture:

p1V1 = n1RT1 and p2 V2 = n 2 RT2

Since

p1 n
V1 = V2 and T1 = T2 ; = 1
p2 n 2

Similarly, p1V1/PTVT = n1RT1/n2RTT; therefore, p1/PT = n1/n T or in its general form:

pi n
= i , or p i = PT y i (1.12)
PT n T

where yi is the mole fraction of the ith component in the total mixture of n compo-
nents. The next relationship provides a way to determine the volume-based concen-
tration of any individual gaseous component

Ci
p i = PT (1.13)
106

where Ci is the concentration of the ith component expressed in ppm.

1.3.5 raoult’s law

Raoult’s law states that the vapor pressure of an ideal solution is directly dependent
on the vapor pressure of each chemical component and the mole fraction of the
Introductory Concepts 13

component present in the solution. Therefore, the individual vapor pressure for each
component is given by the next equation:

p i = Pi*x i (1.14)

where
pi is the partial pressure of the component i in the mixture (in the solution)
Pi* is the vapor pressure of the pure component i
xi is the mole fraction of the component i in the mixture (in the solution)

Equating Equation 1.12 to Equation 1.14, we obtain

P*x i = PT y i

or

P* Yi
= = K i (applied only for ideal mixtures)
PT x i

Therefore,

y i = K ix i (1.15)

where Ki = f(PT, T, and composition of mixture). If, however, Ki is independent of

composition and depends only upon T, then we get the equation known as Henry’s law:

x i = Hip (1.16)

where
xi is the solubility of a gas at a fixed temperature in a particular solvent (in units
of M or mL gas/L)
Hi is Henry’s law constant (often in units of M/atm)
p is the partial pressure of the gas (often in units of atm)

Henry’s law states that at a constant temperature, the amount of a given gas that
dissolves in a given type and volume of liquid is directly proportional to the partial
pressure of that gas in equilibrium with that liquid.

1.3.6 amagat’s law

The volume of a mixture of gases is equal to the sum of the partial volumes of each
component gas. The partial volume of a component gas is the volume in which that
component would occupy at the same T and P.
14 Chemical Engineering Primer with Computer Applications

1.3.7 avogadro’s hypothesIs

• The molecular weight of a gas, in kilograms, occupies 22.4 m3 at STP
(°C, 760 mm Hg).
• The molecular weight of a gas, in grams, occupies 22.4 L at STP.
• The molecular weight of a gas, in pounds, occupies 359 ft3 at NTP (60°F,
760 mm Hg).

END-OF-CHAPTER SOLVED EXAMPLES

Example 1.1

The dimensional formula of a heat transfer coefficient, h, is

[h] = QL-2q-1T -1

In an experimental work on the rate of heat transfer, a value of h = 396 Btu/(ft 2)(°F)

(h) was obtained. Calculate the value of this coefficient in kcal/(m2)(°C)(h)
Solution
From the conversion tables, 1 Btu/kcal = 0.252, 1 ft/1 m = 0.3048, and 1°F/1°C =
1/1.8.
By direct substitution using these conversions,

h = 396 Btu/(ft)2 (°F)(h)

= (369)(0.252)/(0.3408)2 (1/18
. ) kcal/(m)2 (°C)(h)

= 1930 kcal/(m2 )(°C)(h).

Example 1.2

Find the average molecular weight of dry air whose volume-composition is O2

(21%), N2 (78%), and Ar (1%).
Solution

1 2 3 4
Comp % MWt (2) (3)
O2 0.21 32 6.72
N2 0.78 28 21.84
Ar 0.01 20 0.2

Avg. MW 28.76
Introductory Concepts 15

Example 1.3

Calculate the total pressure and the composition of the following gas mixture,
given the partial pressure of each component:

CO2 : 75 mm Hg; CO: 50 mm Hg; N2 : 595 mm Hg; O2 : 26 mm Hg

Solution
Substitution using Equation 1.8 gives the following:

PT = å pi = 75 + 50 + 595 + 26 = 746 mm Hg

Mole fraction of CO2 is obtained using Equation 1.9:

75
XCO2 = = 0.101
746

Similarly, calculations are carried out to find the mole fractions of CO, N2, and O2:
0.067, 0.797, and 0.035, respectively.

Example 1.4

Five hundred pounds of water is flowing a heat exchanger pipe at the rate of
20.0 ft/s. Calculate the kinetic energy of the flowing water in (ft)(lbf ).
Solution

1 2 1 é 1 ù
K.E. = mv = éë(500 lbm )(20 ft/s)2 ùû ê 2 ú
2 2 ë 32.174 (ft)(lbm )/(s )(lbf ) û

K.E. = 3108 (ft )(lbf )

Example 1.5

Calculate the volume of 1 mol of air at 20°C on top of a mountain (altitude 4.2 km),
where the air pressure is approximately 60 kPa.
Solution
Apply Boyle’s and Charles’ laws as successive correction factors to the standard
sea-level pressure of 101.3 kPa:

æ 293 K ö æ 101.3 kPa ö

V2 = (22.4 L) ç ÷ç ÷ = 41 L
è 273 K ø è 60 kPa ø

The standard molar volume 22.4 L/mole is applicable at standard temperature and
pressure STP.
16 Chemical Engineering Primer with Computer Applications

Example 1.6: To Check the Validity of the van der Waals equation

Compare the experimental PV data for propane gas to the predicted values as
shown next:

P = ((R * T)/(V − b)) − (a/V2)

P Experimental A V B R T Predicted P Delta P
8.3 8.61 5 0.0909 0.083 430 6.9 1.4
3.5 8.61 10 0.0909 0.083 430 3.5 0.0
2.5 8.61 15 0.0909 0.083 430 2.4 0.1
2.1 8.61 20 0.0909 0.083 430 1.8 0.3
1.4 8.61 25 0.0909 0.083 430 1.4 0.0
1.4 8.61 30 0.0909 0.083 430 1.2 0.2
1.2 8.61 35 0.0909 0.083 430 1.0 0.2
1.1 8.61 40 0.0909 0.083 430 0.9 0.2
0.8 8.61 45 0.0909 0.083 430 0.8 0.0
0.65 8.61 50 0.0909 0.083 430 0.7 −0.1
0.7 8.61 55 0.0909 0.083 430 0.6 0.1
0.65 8.61 60 0.0909 0.083 430 0.6 0.1

Predicted and experimental pressures as a function of volume

9.0
8.0
7.0 Predicted P
Pressure (atm)

6.0 P experimental
5.0
4.0
3.0
2.0
1.0
0.0
0 10 20 30 40 50 60

Conclusion: The PV values for both experimental and predicted ones match
closely.

Example 1.7

CO is produced by the reaction:

CO2 (g) + C (s) ® 2CO (g)

At equilibrium conditions of 1000°C and a total pressure of 30 atm, 17.0 mole%

of the gas is CO2. If the total pressure is reduced to 20 atm, calculate the CO2
concentration.
Introductory Concepts 17

Solution
pi = PTyi.
PT is the sum of pi = pCO2 + pCO.
First: At 30 atm,

p2CO
Kp =
pCO2

(302 )(0.83)2
= = 1215
. atm.
(30)(0.17)

Second: At 20 atm, KP = 1215 . = p2CO / pCO2 = {20 - pCO2 } /pCO2 .

Solving for pCO2, we obtain pCO2 = 2.55 atm.
Percent CO2 = [2.55/20] × 100 = 12.75.

Example 1.8

Compute the work in joules if a steady force of 3 lbf is needed to push 5 lbm in a
distance of 100 ft.
Solution

Work (W) = Force ´ distance = 3 lbf ´ 100 ft = 300 ft × lbf

= (300 ft × lbf )(1/ 0.7367 J/ft × lbf )

= 406.7 J

Example 1.9

Calculate the molar volume (ft3/lb · mole) and the density (lb/ft3) of methane gas
at 60°F (519.67°R) and a pressure of 3.5 atm. Molecular weight (M) for methane
is 16.04.
Solution

Molar volume = RT/P = [(0.7302 ft 3 × atm/lb × mole × °R)519.67°R(1/3.5 atm)]

= 108.4 ft 3 /lb × mole

Methane density is

(3.5 atm)(16.04 (lb /lbm )

r = (PM) /(RT) =
[(0.7302) (lbmR) /(ft 3 × atm)](519.67)

= 0.148 lb /ft 3
18 Chemical Engineering Primer with Computer Applications

Example 1.10

Calculate the quantity of heat required to raise the temperature of 40 g of ammo-

nia gas from 70°C to 100°C. Specific heat of ammonia is 0.51 Btu/lb · °F.
Solution

Q (heat quantity) = (mass)(specific heat )(DT)

= (40 / 453.6) (lb /g)(0.51) (Btu/lb × °F)30(1.8)(°F / °C)
= 2.4286 Btu

Example 1.11

Find the absolute pressure (mm Hg) of a gas under draft of 5.0 in water. The baro-
metric pressure reads 745.0 mm Hg.
Solution

The draft reading = (5.0 in.)(25.4 mm/in.) (1/13.6 mm Hg/mm water)

= 9.338 mm Hg

Therefore, the absolute pressure in the duct is 745.0 + (−9.338) = 735.66 mm Hg.

REFERENCES
BIPM, n.d. SI Brochure, Section 2.1.1.5, http://www1.bipm.org/en/si/si_brochure/chapter2/
2-1/2-1-1/kelvin.html.
International Bureau of Weights and Measures, n.d., Brief History of the SI, http://www.bipm.
org/en/si/history-si/, retrieved April 21, 2009.
International Bureau of Weights and Measures,” Wikipedia, last modified date Aug. 2, 2016,
https://en.wikipedia.org/wiki/International_Bureau_of_Weights_and_Measures.
 2 Basic Principles
and Introduction
to Calculations
In this chapter, a review of some of the well-known physical and chemical laws is
given in continuation to Chapter 1. In addition, the principles underlying chemical
engineering problems are presented, showing readers how to apply such principles
to the different topics covered in the text.
Definitions of many of the concepts and terms that underlie much of the chemical
and process industries are summarized, such as unit operations and unit processes,
to name a few. Design variables for sizing piping and process equipment are briefly
presented. Systems of units, different temperature scales, and pressure scales are
described.
Much of the materials given in this chapter would add basic knowledge to the
students and enhance the ability in problem solving.
Section I, consisting of Chapters 1 and 2, would pave the way for the readers,
especially when it comes to topics on unit operations and plant design. It may be
considered as a supplement to the chapters found in Section III.

2.1 THE TWO BUILDING BLOCKS OF CHEMICAL

ENGINEERING: UNIT OPERATION AND UNIT PROCESSES
An economical method of organizing much of the subject matter of chemical engi-
neering is based on using the concept of unit operation. This is because of two
reasons:

1. In many chemical processes, each one can be broken down into a series of
steps or operations that are repeated in other processes.
2. These individual steps or operations are based on the same scientific prin-
ciples and guidelines.

A unit operation represents a basic physical operation in a chemical process plant.

Examples are distillation, absorption, fluid flow, heat transfer operations, evapora-
tion, extraction, drying, crystallization, and filtration. Fundamentals pertaining to a
given unit operation are the same regardless of its industrial applications. This is how
pioneers came up with the term unit operation.

19
20 Chemical Engineering Primer with Computer Applications

Unit operations deal mainly with the transfer and the change of both materials
and energy primarily by physical means, arranged as needed by a chemical process.
The following is a partial list of some important unit operations:

• Fluid flow: It deals with the governing principles for flow and transporta-
tion of fluids.
• Heat transfer: It deals with the underlying principles of heat transfer by
different modes.
• Diffusional mass transfer unit operations include distillation, absorption,
extraction, and drying. Separation in these unit operations is accomplished
by the transfer of molecules from one phase to the other by diffusion.

Unit process, on the other hand, involves a chemical conversion of materials in an

industrial chemical plant. A good example will be the reaction of nitrogen with
hydrogen to produce ammonia. A unit process represents the chemical equivalent of
a unit operation, as illustrated next.

Chemical
engineering

Unit operation Unit process

Momentum Heat Mass Reaction

transfer transfer transfer kinetics

2.2 CHEMICAL PROCESS INDUSTRY

Chemical process industry (CPI) is the term that encompasses all chemical-producing
industries. In the CPI, we encounter two types of processes:

1. One process basically involves physical separation or physical changes,

which is the unit operation. Examples include crude oil refining and water
desalination. Here, we have to write material balance (MB) equations to
solve for the unknown parameters.
2. Another process basically involves chemical reaction or chemical changes,
which is the unit process. This includes the manufacture of ammonia,
cement, and others. Here, we have to use the stoichiometric chemical equa-
tions to calculate the yield.
Basic Principles and Introduction to Calculations 21

Many industries would involve a chemical reaction process followed by a physical

separation step. In addition to these distinctive chemical reaction processes or physi-
cal separation operations, other unit operations may be needed.
Physical separation operations (distill, absorption) are known as unit operations that
involve mass transfer between phases. They are called diffusional unit operations (UO).
Within the field of chemical engineering, two broad groups of engineers are
identified:

1. The design and the operation of plants in chemical industry and related
processes. This group is known as chemical process engineers.
2. The development of new chemicals or products ranging from foods and
beverages to cosmetics to cleaners to pharmaceutical ingredients, among
many other products. This group is known as chemical product engineers.

2.3 CHEMICAL PLANT

A chemical plant is one that belongs to the chemical industry. Most processes in the
chemical industry involve a chemical change. The term chemical changes should be
understood to include not only chemical reactions, for example, N2 + 3H2 → 2NH3,
but also physicochemical changes, such as the separation and purification of the
components of a mixture, crude oil fractionation, and water desalination are typical
examples.
In general, chemical plants perform three distinctive functions:

1. Preparation and purification of raw materials

2. Chemical reactions
3. Separation and purification of products

Purely mechanical changes are usually not considered part of the chemical processes.
A chemical plant is schematically shown in Figure 2.1.
As a result of the transformation of raw materials in the presence of energy-
producing finished products, chemical processes are analyzed and studied using the
following chemical engineering tools:

1. Mass and energy balances

2. Thermodynamics
3. Reaction kinetics and catalysis

R. M.
Chemical plant Product
Energy

FIGURE 2.1 Chemical plant with input of raw materials and energy source.
22 Chemical Engineering Primer with Computer Applications

4. Unit operations
5. Instrumentation and control
6. Economics

These six subjects, known as the backbone courses in a typical BS degree curriculum,
are closely dependent on each other, but their principles can be studied individually.

2.4 PROCESS DESIGN

It involves the design of a process for a given desired physical and/or chemical trans-
formation of materials. Process design is the heart of plant design, and it can be
considered to be the summit of chemical engineering, bringing together all of the
components of that field.
Process design covers two distinctive cases:

1. The design of new facilities.

2. The modification or expansion of existing facilities. The design starts at
a conceptual level and ultimately ends in the form of fabrication and con-
struction plans.

A process design includes the following major items:

1. Process flow sheet

2. Mass balance on the overall process and on each unit in the process
3. Energy balance for all units, including heat exchangers requirements
4. Specs of pump capacities, flow, and pressure requirements
5. Specs of size and configuration of chemical reactors, distillation columns,
absorbers, and storage tanks
6. Estimation of utility requirements, such as steam, water, electricity, com-
pressed air, and fuel
7. Economic evaluation that includes an estimate of capital investment, oper-
ating costs, and profitability analysis

2.5 ROLE OF MATERIAL AND ENERGY BALANCES,

THERMODYNAMICS, AND KINETICS
1. Material and energy (M and E) balances: The laws of M and E balances state
that neither mass nor energy can be created or destroyed, but they may be
changed in form. MB is based on the conservation of mass. Similarly, energy
balance (EB) is based on the law of conservation of energy. Often energy
changes in form (observe: carbonate + heat → calcium oxide + carbon dioxide).
2. Thermodynamics: It deals with the transformation of energy from one
form to another (EB is an expression of the first law of thermodynamics).
The second law states that in a process of heat transfer alone, energy may
be transferred only from higher T to a lower T.
Basic Principles and Introduction to Calculations 23

–4.5

–5.0
Straight line
ln[NO2]

–5.5

Data

–6.0

0 60 120 180 240 300 360

Time (s)

FIGURE 2.2 Thermal decomposition of NO2.

Thermodynamics is needed in order to judge the feasibility and efficiency

of a chemical process, using the well-known relationship:

  ΔG = −RT ln k (the value of ΔG has to be negative for a reaction to be feasible)

In other words, given the value of ΔG, calculate k (the chemical reaction
equilibrium constant), hence the composition of phases at equilibrium).
3. Kinetics: This law is used to determine the rate at which a chemical com-
pound reacts, that is, finding the rate of reaction, k. It is needed in the design
of chemical reactors.
4. Kinetics versus thermodynamics.

As stated earlier, the maximum extent to which a chemical reaction can proceed may
be calculated by thermodynamics, which occurs at equilibrium. It follows that the
net rate of a chemical reaction must be zero at this equilibrium point. Thus, a plot of
reaction rate (r) versus time would always approach zero, as the time approaches ∞,
as illustrated in Figure 2.2 for the thermal decomposition of NO2 to NO + O2.

2.6 DESIGN VARIABLES FOR SIZING PIPING

AND PROCESS EQUIPMENT
1. Physical unit operations include the following:
a. Fluid flow in pipes: Noncompressible.
Given: Q (ft3/m) and v (ft/m); you get → Di and then → ΔP
Given: P (fluid pressure) and S (tensile strength of material); you calcu-
late → schedule no, and then determine → t (pipe thickness)
24 Chemical Engineering Primer with Computer Applications

b. Heat transfer: Q = mcpΔt = UAΔTav.

c. Distillation: The variables are N (number of trays), D (column diam-
eter), and R (reflux ratio).
2. Chemical reactors.
The relationship is between three variables: V (volume of reactor, ft3),
θ (residence time, s), and q (flow rate, ft3/s).
Therefore, V = (q)(θ).

2.7 BASIC DEFINITIONS

• Equilibrium constant for a chemical reaction (reversible) is defined as

Concentration of products
k= .
Concentration of reactants

• Distribution constant for a component in a mixture (vapor/liquid equilib-

rium) is defined as K i = yi/xi.
• The three modes of transfer in chemical processes are momentum, heat,
and mass.
• The role of ΔG in chemical reactions is illustrated by the following equa-
tion: ΔG = −RT ln K.
• A differential balance indicates what happens in a system at an instant of
time; each term in the balance is a rate (quantity/time), and it is applied for
a continuous process.
• An integral balance describes what happens between two instants of time.
Each term in the equation is an amount of the balanced (quantity). It is
applied to a batch process.

2.8 CONVERSION OF PHYSICAL EVENTS AND

PRINCIPLES TO MATHEMATICAL FORMULA
As an example, flash distillation problem is shown in Figure 2.3. It is required to cal-
culate the bubble point (BP), the dew point (DP), the flow rates of the streams leaving
the flash distillation column, and their composition.
To illustrate this application, only the calculation of the BP is done, as illustrated next.
Definition: The BP is physically defined as the temperature at which the first bubble
comes out as vapor. One can express this physical statement by saying that å y i = 1,
where yi is the composition of component i in the vapor phase.
Then, we carry on one more step to say that since yi = K ixi, we get å k i x i = 1.
Now, the final mathematical relationship is given by

å k x -1 = f (T
i i BP ),

which goes to zero at the right assumed value of T.

Basic Principles and Introduction to Calculations 25

V
y

F
xF

L
x

FIGURE 2.3 Flash calculation.

This equation represents the mathematical function for the physical statement of
the BP. Therefore, the solution for the BP becomes a trial and error problem by solv-
ing the function, since K i is a function of T or K i = f(Ti).

2.9 BASIC LAWS

Balance equations for momentum, mass, and energy transfer provide the broad foun-
dation for much of the physical problems we encounter in chemical engineering cur-
riculum. They represent important starting steps for developing phenomenological
events especially in dealing with fluid mechanics (momentum transfer), heat and
mass transfer, and reaction studies as well.

2.9.1 mass and energy conservatIon: materIal

Balance and heat Balance
1. The law of conservation of mass, in its most compact form, states that mat-
ter is neither created nor destroyed.
In material balance calculations, it is stated that the total mass of all
materials entering in a process must equal the total mass leaving, plus any
materials accumulating:
Input = Output + Accumulation

At steady-state conditions, Input = Output.

2. The law of conservation of energy (called the first law of thermodynamics),
in its most compact form, states that energy is neither created nor destroyed.

When the two laws are merged together, we get what is known as the law of con-
servation of mass–energy: the total amount of mass and energy in the universe is
constant, where mass and energy can interconvert.
For heat balance calculations for a system, the energy or heat input in the form of
enthalpy processed by materials in, plus any heat added, should be equal to heat out.
26 Chemical Engineering Primer with Computer Applications

2.9.2 thermodynamIcs
The four laws of thermodynamics define the fundamental physical quantities (tem-
perature, energy, and entropy) that characterize thermodynamic systems. The laws
describe how these quantities behave under various circumstances and forbid certain
phenomena (such as perpetual motion):

1. Zeroth law of thermodynamics: If two systems are both in thermal equilib-

rium with a third system, then they are in thermal equilibrium with each
other. This law helps to define the notion of temperature.
2. The first law of thermodynamics: Heat and work are forms of energy trans-
fer. Energy is invariably conserved; however, the internal energy of a closed
system may change as heat is transferred into or out of the system or work is
done on or by the system. It is a convention to say that the work that is done
by the system has a positive sign and connotes a transfer of energy from the
system to its surroundings, while the work done on the system has a nega-
tive sign.
3. The second law of thermodynamics: An isolated system, if not already in
its state of thermodynamic equilibrium, spontaneously evolves toward it.
Thermodynamic equilibrium has the greatest entropy among the states
accessible to the system. Perpetual motion machines of the second kind are
thus impossible.
4. The third law of thermodynamics: The entropy of a system approaches
a constant value as the temperature approaches zero. The entropy of a
system at absolute zero is typically zero and, in all cases, is determined
only by the number of different ground states it has. Specifically, the
entropy of a pure crystalline substance at absolute zero temperature is
zero.

2.9.3 some general tIps

2.9.3.1 Parts-Per Notation (Schwartz and Warneck, 1995)
The parts-per notation is a unit that deals with very small traces of species within a
mixture of gases or liquids. Parts-per million (ppm) and parts-per billion (ppb), as
well as parts-per trillion (ppt) (American definition of trillion 1012), refer to mass or
mole ratios and communicate how many parts of the species are present per million,
billion, or trillion parts of the mixture. Generally, mass ratios are used when dealing
with liquids and mole ratios are used when dealing with gases.
For example, let us say the air around us contains 20 ppm He (helium). This
means that, if one assumes that a molar basis is being used, for every million moles
of air, there are 20 moles of helium. If the example was in terms of ppb, this would
mean that for every billion moles of air, there are 20 moles of He.
Basic Principles and Introduction to Calculations 27

2.9.3.2 Frequently Asked Questions

• What is the difference between distillation and evaporation?
Hint: Recovery of glycerin from dilute solution as a by-product in soap
making.
• How do you determine if a chemical reaction is feasible to carry on?
Hint: Calculate ∆G.
• The chemical engineer, in general, is interested not so much in the state of
equilibrium as in the rate at which a process is taking. Explain?
Hint: At equilibrium the driving force  =  zero.
• Differentiate between the concept of equilibrium in chemical and physical
systems.
Answer: For the reversible reaction, A + B <––> C, K (reaction rate) = [C]/
[A] · [B], while for distillation, the distribution constant is K i = yi/xi.
• Define the roles of kinetics and thermodynamics in chemical engineering.
Answer: While chemical kinetics is concerned with the rate of a chemical
reaction, thermodynamics determines the extent to which reactions occur,
that is, to find the yield at equilibrium. In a reversible reaction, chemical
equilibrium is reached when the rates of the forward and reverse reactions
are equal (the principle of detailed balance) and the concentrations of the
reactants and products no longer change.
• What are the main six categories of chemical reactions?
Answer: (1) Combustion, (2) Synthesis, (3) Decomposition, (4) Single dis-
placement, (5) Double displacement, and (6) Acid base
• Describe what is meant by the following: (a) Isothermal process, (b) Isobaric
process, (c) Isometric process, (d) Adiabatic process, and (e) Isentropic
process
Answer: (a) dt = 0, constant T, (b) dP = 0, constant P, (c) dV = 0, constant V,
(d) Q = 0, (e) constant entropy

END-OF-CHAPTER SOLVED EXAMPLES

Example 2.1

Sodium sulfite is used to remove dissolved oxygen from boiler-feed water to avoid
corrosion, as given by the equation:

2 Na2SO3 + O2 → 2Na2SO4

As a chemical engineer in charge of the utilities department, calculate how many

pounds of S.S. are required theoretically, to remove dissolved O2 from 1 million
gallon of feed water that contains 10.0 ppm of O2?
28 Chemical Engineering Primer with Computer Applications

Children Face Tough Issues

Children
Issues
Issues Issues
Face Tough Face Tough Issues

Children Face Tough Issues

Face Tough Issues Children Face Tough Issues

Face Tough Issues Issues

Example 2.2

CO is produced by the reaction:

CO2 (g) + C (s) ® 2CO (g)

At equilibrium conditions of 1000°C and a total pressure of 30 atm, 17.0 mole%

of the gas is CO2. If the total pressure is reduced to 20 atm, calculate the CO2
concentration.
Solution
pi = PTyi.
PT is the sum of pi = pCO2 + pCO.
First: At 30 atm,

p2CO
Kp =
pCO2

(302 )(0.83)2
= = 1215
. atm.
(30)(0.17)

2
Second: At 20 atm, KP = 1215 . = pCO /pCO2 = {20 - pCO2 }/pCO2.
Solving for pCO2, we obtain pCO2 = 2.55 atm.
Percent CO2 = [2.55/20] × 100 = 12.75.

Example 2.3

Calculate the volume of 1 mol of air at 20°C on top of a mountain (altitude 4.2 km),
where the air pressure is approximately 60 kPa.
Solution
Apply Boyle’s and Charles’ laws as successive correction factors to the standard
sea-level pressure of 101.3 kPa:
Basic Principles and Introduction to Calculations 29

293 K 1013
. kPa
V2 = (22.4 L/mole)
273 K 60 kPa

= 41L

The standard molar volume 22.4 L/mole is a value that it is valid only at STP.

Example 2.4

For the industrial production of CO2, fuel oil is injected into a furnace to be burned
with exactly 1.5 times the theoretical amount required for complete combustion.
Calculate the exact composition of the stack gases, and determine the CO2 purity
of the product to be sold. For simplicity, assume the fuel oil to be C12H26.
Solution

C12H26 + 18.5O2 12CO2 + 13H2O

Using 100 kg · mole of fuel oil as a basis:
O2 required = 1.5 × 18.5 × 100 = 2775 kg · mole
N2 in with the O2 = 10,307 kg · mole
Excess O2 = 2775 − 1850 = 925 kg · mole
Results based on 100 kg · mole of fuel are as follows:

Products kg · mole %
CO2 (100)(12) = 1,200 1,200/13,732 = 8.7
H2O (100)(13) = 1,300 9.5
O2 925 6.7
N2 10,307 75.1
Total 13,732 100

Example 2.5

It is required to concentrate an extracted orange juice using vacuum evaporator.

Conditions of input and output are as indicated in the diagram.

W kg/h water

1000 kg/h, feed

(juice: 7.08 solids) Evaporator

B kg/h con. juice (58% solids)

Choosing 1000 kg/h as a feed, calculate the values of W and B.

30 Chemical Engineering Primer with Computer Applications

Solution
This is a physical separation process. We have two unknowns to calculate by using
total MB (TMB) and component MB (CMB).
TMB:

1000 = W + B (2.1)

CMB on solids:

1000 (0.0708) = W(0.0) + B(0.58) (2.2)

Solving the two equations in two unknowns, we obtain W = 878 kg/h and
B = 122 kg/h.

Example 2.6

Combustion of heptane (C7H16) is used as a source to produce dry ice. Calculate

how many kilograms of heptane must be burned to produce 500 kg of dry ice,
assuming that 50% of the CO2 is converted into dry ice.
Solution
The chemical equation of the combustion of heptane states the following:

1mole C7H16 + 11mole O2 ® 7 mole CO2 + 8 mole H2O1.

Therefore, (500 kg dry ice)(1 kg CO2/0.5 kg dry ice)(1 kg · mole CO2/44 kg CO2)

(1 kg · mole C7H16/7 kg · mole CO2)(100 kg C7H16/1 kg · mole C7H16) = 325 kg C7H16.

Example 2.7

Calculate the kinetic energy of a missile moving at 12,000 mile/h above the earth,
with an acceleration due to gravity of 30 ft/s2.
Solution
We arbitrarily take 1 lb mass as a basis.

1 2
K.E. = mv
2
1
= (1 lbm )[1 lbf × (s2 ) / 32.2 ft × lbm ][(12, 000 miles)2 /h2 ]
2
´ [(5280 ft )2 /mile2 ][h2 /(3600 s)2
= 4.81 ´106 (ft)(lbf )
Basic Principles and Introduction to Calculations 31

Example 2.8

The well-known equation to calculate the pressure drop due to friction losses for
fluids in pipes is given by ΔP = [2fLρv2/D], where ΔP is the pressure drop, v is the
velocity, L is the length of pipe, ρ is the density of fluid, and D is the diameter of pipe.
Find out if this equation is dimensionally consistent. Support your answer.
Solution

DP = [2fLrv2 /D] = (ft /ft )(lbm /ft 3 )(ft /s)2[lbf × (s2 ) /lbm × ft ]
= lbf /ft 2

The equation is consistent as far as the dimensions are concerned; f is dimensionless.

Example 2.9

Lithium hydroxide is capable of removing CO2 by absorption, particularly for

manned spacecraft according to the following reaction:

2LiOH(s) + CO2 ® LiCO3 (s) + H2O

Assuming that 1 kg of CO2 is released per day per person, calculate the amount
of LiOH required.
Solution
Basis 1 kg CO2

[1kg CO2 ][1kg × mole CO2 /44.01kg CO2 ][2 kg × mole LiOH/1kg × mole CO2 ]

[23.94 kg LiOH/1kg × mole LiOH] = 2.18 kg LiOH

Answer: 2.18 kg LiOH per day per person is needed.

Example 2.10

A solvent recovery system delivers an inert gas, saturated with benzene vapor
(C6H6). This gas is at 70°F and 750 mm pressure. The gas is compressed to 5 atm
and cooled to 70°F, after compression.
Calculate how many pounds of benzene are condensed per 1000  ft3 of the
feed gas. The vapor pressure of benzene at 70°F is 75 mm.

Feed gas

Benzene
32 Chemical Engineering Primer with Computer Applications

Solution
The basis is 1000  ft3 of feed gases consisting of benzene plus inert. Applying
volume % = pressure %, where the total pressure is 750 mm, while the partial
pressure of benzene is 75 mm, the volume % of the inert = (750 − 75)/750.
The volume of inert gas in the feed = (1000)(750 − 75)/750 = 900 ft3.
Then the volume of benzene = 100 ft3.
Convert the volumes to moles: moles of inert = 2.3 and moles of benzene =
0.2556.
The ratio of benzene to inert, before compression, is 0.2556/2.3 = 0.1111.
Now after compression and cooling, a portion of benzene will condense and
be separated. Ratio will be 75/[(760 × 5) − 5] = 0.0201. Hence (0.1111 − 0.0291) =
0.0910 mole of benzene is condensed per mole of inert.
For 2.3 mol of inert, benzene separated is 0.0910 × 2.3 × 78.1 = 16.35 lb.

REFERENCE
Schwartz, S.E. and Warneck, P. Units for use in atmospheric chemistry. Pure &
Applied Chemistry 67: 1377–1406, 1995. Retrieved on March 9, 2011, http://
www.iupac.org/publications/pac/1995/pdf/6708x1377.pdf.
Section II
Fundamentals and
Problem-Solving Profile
Chapter 3 Numerical Methods and Chemical Engineering Computations
Chapter 4 The Approach to Solve Problems
Section II encompasses Chapters 3 and 4. Chapter 3, “Numerical Methods and
Chemical Engineering Computations,” is devoted to the introduction of numerical
methods, which are often divided into two main categories:

1. Elementary ones such as finding the root of an equation, integration of a

function or solving a set of linear equations.
2. Intensive ones which are often needed for the solution of practical problems.

Emphasis in Chapter 3 is placed on elementary methods, mostly used in arithmetic

operations. Basic applications with many examples are presented, using MATLAB®
and Excel. We may call this is the fundamental part in numerical analysis.
Chapter 4, “Approach to Solve Problems by Computers,” illustrates how to tackle
a solution of a problem. Modeling and simulation are principal approaches for the
quantitative description of chemical engineering processes in solving problems.
Methodology and problem solving guidelines are described.
Basic applications with more than 15 examples are presented in Chapters 3 and 4.
The solutions to these examples are obtained using MATLAB and Excel. MATLAB is
a powerful code-based mathematical and engineering calculation program. It performs
all calculations using matrices and vectors in a logical programming environment.
In addition, a set of application problems for Section II is included in Appendix A.
 3 Numerical Methods and
Chemical Engineering
Computations
The assumption of an absolute determination is the essential foundation of every
scientific enquiry.
(Heilbron, 2000)

One of the main objectives of Chapters 3 and 4 (Section II) is to devise, evaluate, and
apply numerical techniques for employing computers to solve problems in chemi-
cal engineering. In Chapter 3, numerical methods are introduced with emphasis on
elementary applications. Definitions of basic concepts are given; areas and domain
of numerical methods are identified; and basic applications for many examples are
presented.

3.1 INTRODUCTION
Computer scientists, programmers, and technology support staffs take a very dif-
ferent view of the computer from other users. They must know the details of how
operating systems work and how to code various scripts that control function. They
must be able to control the low-level details that a user simply assumes.
The focus of numerical methods is simply translating engineering problems into
algorithms and implementing them using computers. Numerical method is a branch
of applied mathematics, concerned with methods for solving complicated equa-
tions using arithmetic operations, often so complex that they require a computer, to
approximate the analysis process. Numerical analysis naturally finds applications in
all fields of engineering and the physical sciences. It is an important underpinning
for techniques used in computational science in general. In other words, using com-
puters to solve problems is automatically tied up to numerical techniques.
In the development of numerical methods, simplifications need to be made to
progress toward a solution. For example, general functions may need to be approxi-
mated by polynomials, and computers, on the other hand, cannot generally represent
numbers exactly. Therefore, numerical methods do not usually give the exact answer
for a given problem at hand. However, it could be stated that the overall goal of the
field of numerical analysis is the design and analysis of techniques to give approxi-
mate but accurate solutions to problems.

35
36 Chemical Engineering Primer with Computer Applications

3.2 BASIC DEFINITIONS AND INTRODUCTORY REMARKS

The subject of numerical methods is the study of quantitative approximations to the
solutions of mathematical problems including consideration of and bounds to the
errors involved.
The arithmetic model used is called algorithm, the set of procedures the computer
executes is called program, and the commands that carry out the procedures are
called code.

3.2.1 algorIthms
According to Blass and Gurevich (2003), an algorithm is defined as an effec-
tive method expressed as a finite list of well-defined instructions for calculating a
function. Starting from an initial state and initial input, the instructions describe a
computation that, when executed, proceeds through a finite number of well-defined
successive states, eventually producing output and terminating at a final ending state.
In computer systems, an algorithm is basically an instance of logic written in
software by software developers to be effective for the intended target computer(s)
for the target machines to produce output from given input (perhaps null).
Algorithms resemble recipes, which tell you how to accomplish a task by per-
forming a number of steps. For example, to bake a cake the steps are as follows:
preheat the oven; mix flour, sugar, and eggs thoroughly; pour into a baking pan; and
so forth.
Algorithms were originally born as part of mathematics. The word algorithm
comes from the Arabic writer Muhammad ibn Mūsā al-Khwārizmi, but currently the
word is strongly associated with computer science.

3.2.2 programmIng language

Programming languages must provide a notational way to represent both the process
and the data. Although many programming languages and many different types of
computers exist, the important first step is the need to have the solution. Without an
algorithm, there can be no program.

3.3 AREAS AND DOMAIN OF NUMERICAL METHODS

Numerical analysis is widely used in many chemical engineering computations. Due
to the use of computers, cumbersome calculations can be done easily and a solution
is reached in a shorter time. Applications include the following:

1. Numerical solution of systems of linear equations: This refers to solving for

x in the equation Ax = b with given matrix A and column vector b. Solving
for x = A−1b.
2. Numerical solution of systems of nonlinear equations: This refers to root-
finding problems that are usually written as f(x) = 0, with x a vector with n
Numerical Methods and Chemical Engineering Computations 37

components and f(x) a vector with m components. The most important case
is where n = m.
3. Trial and error procedures: This refers to solution of equations using the
iterative convergence methods (Newton’s method).
4. Problems that require numerical differentiation/integration.
5. Optimization: This refers to minimizing or maximizing a real-valued func-
tion f(x). The permitted values for x = (x1,…,xn) can be either constrained
or unconstrained. The linear programming problem is a well-known and
important case; f(x) is linear, and there are linear equality and/or inequality
constraints on x.
6. Use computable functions p(x) to approximate the values of functions f(x)
that are not easily computable or use approximations to simplify dealing
with such functions. The most popular types of computable functions p(x)
are polynomials, rational functions, and others.
7. Regression and correlation of a given set of data.

3.4 APPLICATIONS USING ELEMENTARY NUMERICAL METHODS

This section encompasses a set of solved examples to illustrate some of the basic
applications of the numerical techniques. Whenever it is difficult, for example, to
integrate, differentiate, or determine some specific value of a function, a computer
may be called upon to numerically approximate the desired solution. In the case
of integration, finding the area under a curve is a useful tool in a large number of
problems in many areas of science, especially in engineering. For a curve produced
by a function, you may be able to integrate the function from, say, point a to point
b and calculate the area under the curve in that way. However, for curves produced
from data or for curves that are produced by some complicated functions, analytical
integration may not be possible. Solution could be done in a number of ways, but one
easy way is to employ Excel or use MATLAB®.
Both Excel and MATLAB provide the following types of functions for perform-
ing mathematical operations and data analysis:

• Matrix manipulation and linear algebra

• Polynomials and interpolation
• Optimization
• Differentiation and integration
• Data analysis and statistics
• Ordinary differential equations
• Solution of a single nonlinear algebraic equation

By examining the following examples presented in this section, we will attempt to

demonstrate the application of these principles, followed by a set of problems. This
approach will introduce students to solve more advanced practical chemical engi-
neering problems with no barrier whatsoever. Computations, using MATLAB and
Excel, are demonstrated as well in Chapters 6, 7 & 8.
38 Chemical Engineering Primer with Computer Applications

END-OF-CHAPTER SOLVED EXAMPLES

Example 3.1: An Algorithm, Find Max

Given: A list of positive numbers.

Find: The largest number on the list.
Inputs: A list L of positive numbers. This list must contain at least one number.
(Asking for the largest number in a list of no numbers is not a meaningful question.)
Outputs: A number n, which will be the largest number of the list.

Algorithm

• Set max to 0.
• For each number x in the list L, compare it to max. If x is larger, set max
to x.
• max is now set to the largest number in the list.
• end
• max
• else
• disp(‘insert a correct set of numbers!’)
• end

Example 3.2: Newton–Raphson Method (Algorithm)

In calculus, Newton’s method is an iterative method for finding the roots of a

differentiable function (i.e., solutions to the equation). Given a function f defined
over the real x and its derivative f′, we begin with a first guess x0 for a root of the
function f. Provided the function satisfies all the assumptions made in the deriva-
tion of the formula, a better approximation x1 is x1 = x0 − f(x0)/f′(x0).
Geometrically, (x1, 0) is the intersection with the x-axis of the tangent to the
graph of f at (x0, f(x0)). The process is repeated as xn+1 = xn – f(xn)/f′(xn)… until a
sufficiently accurate value is reached.
Consider the problem of finding the square root of a number. For example, if
one wishes to find the square root of 612, this is equivalent to finding the solution
to x2 = 612. Therefore, the function to use in Newton’s method is f(x) = x2 − 612
and then f′(x) = 2x.
With an initial guess of 10, the sequence given by Newton’s method is

x1 = x0 - f(x0 )/f ¢(x0 ) =10 - [(10)2 - 612]/2(10) = 35.6

x5 = 24.73863375376 (final answer)

Example 3.3: Integration

Create the function f(x) = e−x2(ln x)2.

fun = @(x) exp( x. ^ 2).*log(x). ^ 2;

Numerical Methods and Chemical Engineering Computations 39

Evaluate the integral from x = 0 to x = lnf.

q = integral (fun,0,Inf)

q = 1.9475

Example 3.4: Differentiation

We are going to develop a MATLAB® function to calculate the numerical deriva-

tive of any unidimensional scalar function fun(x) at a point x0. The function is
going to have the following functionality:
Usage: D = Deriv(fun,x0)
fun: Name of the unidimensional scalar function
x0: Point of interest (scalar)
D: Derivative of fun at x0 (scalar)
Now, let us try our derivative function. We create a function in a separate
m-file:
function y = inverse(x): Y = 1/x. And we can call it like this: Deriv(‘inverse’, 1)
The result: Expected: −1, Obtained: −1.0000

Example 3.5: Solution Using Matrix

Solve the following system of equations for x, y, and z by using the matrix method:

10x + 3y + 5z = 8

8x + 2y + 2z = 7
3x + 4y - z = 6

Solution

A = [10, 3, 5; 8, 2, 2; 3, 4, - 1];

B = [8; 7; 6];

X = A\B;

x = X(1), y = x(2), z = X(3)

Gives the result

x = 0.7917

y = 0.7917

z = -0.4583
40 Chemical Engineering Primer with Computer Applications

Example 3.6

The experimental values calculated for the heat capacity of ammonia from 0 to
500 are as follows:

T (°C) Cp (cal/g · mole · °C)

0 8.371
18 8.472
25 8.514
100 9.035
200 9.824
300 10.606
400 11.347
500 12.045

(a) Fit the data for the following function:

Cp = a + bT + CT2 + DT3

where T is in °C
(b) Calculate the amount of heat Q required to increase the temperature of
150 mol/h of ammonia vapor from 0°C to 200°C if you know that

Tout

Q=n
ò Cp dt
Tin

Solution
T =[0,18,25,100,200,300,400,500]

Cp =[8.371,8.472,8.5149
, .035,9.82410
, .60611
, .347,12.045]

P = Polyfit(T,Cp,3)

n = 150; syms t

Cpf = P(4) + P(3)*t + P(2)*t2 + P(1)*t3;

Q = n*int(Cpf,0.200)
2.7180e+005

Example 3.7: Solution of a System of Linear Equations by excel

5x + 1y + 8z = 46
4x - 2y = 12
6x + 7y + 4z = 50
Numerical Methods and Chemical Engineering Computations 41

In matrix notation, this can be written as AX = B

é5 1 8ù éx ù é 46ù
ê ú ê ú ê ú
with A = ê 4 -2 0ú , X = êy ú , B = ê12 ú
êë6 7 4úû êë z úû êë50 úû

If A−1 (the inverse of A) exists, we can multiply both sides by A−1 to obtain X =
A−1B. To solve this system of linear equations in Excel, execute the following steps:

Example 3.8: Finding the Acid Concentration

Parts of a centrifugal pump are dipped in an acid–water bath to clean them. By

time, the acid–water concentration decreases because of loss of solution as the
parts are removed. The bath concentration should not go beyond 50%.
Starting with 90% acid–water concentration, assume that 1% of the solution is
removed with every part cleaned.
Find: How many parts, n, can be cleaned in the bath?
Given: Initial concentration = 90%
Final concentration = 50%
Usage rate = 1%/part cleaned
42 Chemical Engineering Primer with Computer Applications

Solution
log(initial con + min con)
n=
log[1 + lost% / 100]

 initial _ con = 90;

 min _ con = 50

 lost = 0.01

 n = floor(log(initial_ con/min _ con)/log(1  lost)

 n = 59

Example 3.9: Radioactive Decay of Polonium

Polonium has a lifetime of 140 days. Starting with 10 g today, calculate how much
is left after 250 days?
Solution
Amount left = initial amount (0.5)time half  time
≫ initial _ amount = 10;
 half _ life = 140; time = 250 ;

 amount left = initial amount ^_0.5 ^(time/half life)

 amount _left = 2.9003

Example 3.10

Solve the following system of equations for x, y, and z by using the matrix method

10x + 3y + 5z = 8
8x + 2y + 2z = 7
3x + 4y - z = 6

Solution

A = [10,3,5; 8,2,2; 3,4, - 1]; B = [8; 7; 6];

x = X(1),y = X(2),z = X(3)

x = X(1),y = X(2),z = X(3)

Numerical Methods and Chemical Engineering Computations 43

Gives the results

x = 0.7917
y = 0.7917
z = -0.4583

Example 3.11

Estimate the average density of a water–ethanol mixture at different water com-

positions knowing that
Water density = 1000 kg/m3
Ethanol density = 780 kg/m3
Mixture density = Xwater × water density + Xethanol × ethanol density
Solution
Pwater = 1000;
Pethanol = 780;
Xwater = 0:.1:1
Xethanol = 1 - Xwater
Pav = Pwater*Xwater + Pethanol*Xethanol

Xwater
= 0 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000
0.7000 0.8000 0.9000 1.0000

Xethanol
= 1.0000 0.9000 0.8000 0.7000 0.6000 0.5000 0.4000
0.3000 0.2000 0.1000 0

Answer : rav
= 780 802 824 846 868 890 912
934 956 978 1000

REFERENCES
Blass, A. and Gurevich, Y. Algorithms: A quest for absolute definitions. Bulletin of
European Association for Theoretical Computer Science 81. http://research.microsoft.
com/~gurevich/Opera/164.pdf, 2003. Retrieved July 2012.
Heilbron, J.L. The Dilemmas of an Upright Man. Max Planck and the Fortunes of German
Science, With a New Afterword, Harvard University Press, 2000.
 4 The Approach to Solve
Problems by Computers
An experiment is a question which science poses to Nature and a measurement is the
recording of Nature’s answer.
(Planck, 1903)

The main objective of this chapter is to learn how to set up and validate mathemati-
cal models in order to solve chemical engineering problems. The implementation of
models in a structured programming language such as MATLAB® or using spread-
sheets is presented.
Model process development and mathematical formulation is detailed in this
chapter. Applications covering numerous examples are also included.

4.1 INTRODUCTION
Learning how to solve problems is an important part of developing competency in
science and engineering. It is worth noting that most engineering problems are based
upon one of three underlying principles:

1. Equilibrium, force, flux, and chemical

2. Conservation laws: Energy and mass
3. Rate phenomena

The solution of chemical engineering problems should be an integrated part of this

text, since the principles of chemical engineering are introduced along with solving
numerical problems.
In attempting to solve a problem, we will demonstrate how students can attack a
problem. The next proposed procedure is an attempt to be followed:

• Identify the type of problem at hand, as shown next:

45
46 Chemical Engineering Primer with Computer Applications

(1) (2) (3)

Problems that Simple problems Problems handling

involve basic that require to set advanced process
conversion of up M.B. and/or H.B. and design
units and others around a system computations

Process Design
calculations calculations
include two main and
categories computation

Physical Chemical
operations: reactions:
e.g., evaporat., use mole
distillat. balance

Physical Chemical
operations processes

• Find out, for the problem as identified in the first procedure, if you need
additional help from the sources available at your fingertip (found in the
text).

4.2 METHODOLOGY
One of our main objectives in this primer is to demonstrate how to solve chemical
engineering problems that require numerical methods by using standard algorithms,
such as MATLAB or spreadsheets. To say it in simple words, it is to device and
evaluate numerical techniques for employing computers to solve problems in chemi-
cal engineering.
Problem solving using computers could be handled by using

• Spreadsheets, such as Excel

• A programming language such as MATLAB

A spreadsheet such as Excel is a program that let you analyze moderately large
amounts of data by placing each data point in a cell and then perform the same
operation on groups of cells at once. One of the advantages of spreadsheets is that
data input and manipulation are relatively intuitive and hence easier than doing the
same tasks in MATLAB (Towler and Sinnott, 2013).
The Approach to Solve Problems by Computers 47

Details on using Excel showing how to input and manipulate data and perform
operations and others are fully explained in many references found in the open
literature.
Spreadsheet software has become indispensable tools in solving chemical engi-
neering problems because of the availability of personal computers, ease of use, and
adaptability to many types of problems. Handheld calculations are encouraged as
well to learn a numerical technique in solving a problem.
The following basic four steps are normally involved in solving problems by
computers:

1. Go to refresher in
2. Formulation of the
Start Text for Ch.E.
Problem: Given, Find?
Fundamentals

3. Selection of an
Algorithm to solve your
problem

4. Computation

End

4.3 MODEL DEVELOPMENT AND MATHEMATICAL

FORMULATION
The basic types of problems, we encounter in formulating mathematical modeling,
fall into three main categories:

1. Equilibrium problems: This type of problems is recognized as steady state,

where a solution does not change with time.
2. Eigenvalue problems: This type of problems is recognized as extensions of
equilibrium problems in which critical values of certain parameters are to
be determined in addition to the corresponding steady-state configuration.
3. Transient, time-varying, or propagation problems: This type of problems
is concerned with predicting the subsequent behavior of a system from the
knowledge of the initial stage.
48 Chemical Engineering Primer with Computer Applications

Mathematical treatment involves four basic steps, as shown next:

Formulation Solution Interpretation Refinement

Formulation step
may result in:

An algebraic eq., difference eq.,

differential eq., integral eq., or a
combination of these.

Modeling and simulation are principle approaches for quantitative description of

chemical engineering processes in solving problems.
Quantitative process description is advantageous on two grounds:

1. From a scientific point of view: It addresses the process mechanism study,

which leads to the creation of a hypothesis about the process description.
This is followed by a mathematical model.
2. From an engineering aspect: It forms the basis of an engineering aspect of a
chemical process or a chemical plant. The Association for the Advancement
of Modeling and Simulation Techniques in Enterprises (AMSE) gives the
following definitions:
a. The purpose of modeling is a schematic description of the processes
and the systems.
b. The simulations are employments of the models for process investi-
gations or process optimizations, without experiments with real sys-
tems. The introduction of interactive software packages brought about
a major breakthrough in chemical engineering computations.

The solution of a problem is illustrated next:

Computer
Input Output: Solution

Select arithmetic model (algorithm) and programing

Data and problem definition: Given/Find

The Approach to Solve Problems by Computers 49

The following three steps are basically applied in this procedure:

1. Understanding the physical principles underlying the process involved in

the problem in order to build a conceptual model.
2. Manipulation and formulation of these principles into a mathematical
expression or a correlation, that is, a mathematical model. This is achieved
by a thorough analysis of the engineering problems at hand, which may
involve two types:
a. Mathematical formulation (modeling) of engineering problems corre-
sponding to specific physical situations such as momentum, heat and
mass transfer, chemical reactions, and thermodynamics.
b. Conversion of physical events and principles (e.g., a material balance) to
mathematical model.
3. In engineering practice, numerical values must be incorporated and a prac-
tical solution is obtained.

These steps are presented by Figure 4.1, which illustrates different options of numer-
ical methods involved in solving problems.

Ax = b Linear

X= A–1b Other

Conceptual model
for a physical event or a Mathematical ODE
stated principle model

Nonlinear

Newton’s method: f(x) = 0

xn+1 = xn – f(xn)/f΄(xn)

FIGURE 4.1 Formulation of mathematical model through numerical methods.

50 Chemical Engineering Primer with Computer Applications

4.4 APPLICATIONS
To demonstrate the earlier procedure, the problem of flash distillation is considered.
Flash calculations are very common, perhaps one of the most common chemical
engineering calculations. They are a key component of simulation packages like
Hysys and Aspen.

4.4.1 proBlem statement

It is required to calculate the bubble-point (BP) temperature, the dew-point tempera-
ture (DP), and the flow rates of the streams leaving the flash distillation column as
well as their composition. Mathematical formulation to determine the BP is done
first through the following analysis.
Definition: The BP temperature is physically defined as the lowest temperature
at which the first bubble comes out as vapor, when the liquid is slowly heated at
constant pressure. Mathematically, at the BP, the following relationships hold: (a)
å y i = 1.0 and (b) å p i = PT .
V
y

F
xF

L
x

Now, mathematical formulation is pursued through these two equivalent definitions for
the BP temperature. But let us first present the following fundamental relationships:

• Raoult’s law: For a gas–liquid mixture, the partial pressure of component

“i” in the liquid phase is given by

p i = Pi0 x i (4.1)

• Dalton’s law: In the vapor phase, where the vapor is in equilibrium with the
liquid, the partial pressure of component, i, is

p i = PT y i (4.2)

Take the sum of both sides of Equation 4.2:

åp = P i T
The Approach to Solve Problems by Computers 51

where
pi is the partial pressure of component i
Pi0 is the vapor pressure of pure component i
PT is the total pressure

Equating Equations 4.1 and 4.2, we obtain

y i Pi0
= = Ki (4.3)
x i PT

• Antoine’s equations: The Antoine equation is a simple three-parameter fit to

experimental vapor pressures measured over a restricted temperature range:
B
Log P 0 = A -
T+C

where
A, B, and C are Antoine coefficients that vary from substance to substance
P is the vapor pressure of the pure component

1. Determination of BP using the definition given in terms of the sum of yi, by

the Equation (a): å y i = 1.0, as shown in Figure 4.2. The following equation
represents this case, where éë å y i ùû is rewritten in terms of the xi’s, (yi = kixi):

f (Tassu ) = éê
ë å k x ùûú -1 goes to zero at T
i i assu = TBP (4.4)

2. Determination of BP using the definition in terms of the sum of pi, as per

the Equation (b): å
p i = PT , as shown in Figure 4.3.

At the BP, the sum of partial pressure of the components should be equal to the
total pressure on the system, P T, or f (Tassu ) = {[ å p i ] - PT} goes to zero at Tassu = T BP.

Calculate Pi0 using:

Start: Tassu Calculate
B
Log P0 = A – yi = [Pi0/PT](xi)
T+C

Check on the Σyi = 1.0

or f(Tassu) = {[Sum of yi]–1} Goes to 0
NO ?
when Tassu = TBP?

YES

FIGURE 4.2 Determination of TBP using Equation (a).

52 Chemical Engineering Primer with Computer Applications

Calculate Pi0 using: Calculate

Start: Tassu
B Sum of [xi Pi0]
Log P0 = A –
T+C

Calculate:

f (Tassu) = {[Sum of xiP0]–PT}

Find out if f(Tassu)

NO Goes to
zero ?

YES

FIGURE 4.3 Determination of TBP using Equation (b).

Using Equation 4.1 to replace pi,

{ åx P úûù - P } goes to zero at T

f (Tassu ) = êé
ë i
0
T assu = TBP (4.5)

The solution of these nonlinear algebraic equations for the BP, Equations 4.4 and 4.5,
using MATLAB, is presented in the following examples.
Similarly, the DP temperature is physically defined as the temperature at which
the first liquid drop would form when the temperature of a mixture of vapors is
slowly decreased (cooled) at a specified constant pressure.

END-OF-CHAPTER SOLVED EXAMPLES

Example 4.1

For a three-component mixture, the following information is available:

Component Number Ki Composition (xi): Mole Fraction

1 K1 = (0.01T)/P 1/3
2 K2 = (0.02)/p 1/3
3 K3 = (0.03)/P 1/3
The Approach to Solve Problems by Computers 53

Compute the BP temperature, TBP at the specified pressure of 1 atm by using

Newton’s method. Take the first assumed value for Tn be equal to 100°F.
Manual Solution
Assuming T1 = 100°F and P = 1 atm. The following calculation is carried out for
the first trial:

Component xi Ki at 1 atm and T = 100°F (Ki)(xi) [dK i /dT]Tn=100 (xi)(dki/dT)

1 1/3 1 1/3 0.01 (0.01)/3
2 1/3 2 2/3 0.02 (0.02)/3
3 1/3 3 3/3 0.03 (0.03)/3
∑ 1.0 6/2 = 3 0.06/3 = 0.02

From these results, it follows that

f(100) = [å Kixi ] - 1.0 = 2 - 1 = 1

and

dKi
f ¢(100) = å xi = 0 .0 2
dT

where f′ stands for the first derivative of the [å xidKi ] w r t T.

Applying the Newton’s formula,

ì f (T ) ü
T2 = T1 – í 1 ý
î f ¢(T1) þ
æ 1 ö
= 100 – ç ÷
è 0.02 ø
= 50°F

Carry on one more trial to check the final answer.

Solution by Excel

B C D E F G H I J K L
T1 Component Xi Ki XiKi [dKi/dT]Tn (xi)(dki/dT)
100 1 1/3 1 1/3 0.01 1/300
2 1/3 2 2/3 0.02 1/150
3 1/3 3 1 0.03 1/100
∑ 6 1 6 2 0.06 0.02

f(100) = [∑KiXi] – 1 1
f΄(100) = ∑ XidKi/dT 0.02
0
T2 = T1–[f(T1)/f΄(T1)] 50 F
54 Chemical Engineering Primer with Computer Applications

Example 4.2

An equimolar vapor mixture of benzene and ethylbenzene is kept at 100°C.

Calculate the pressure at which the first drop of liquid will form and its
composition.
Solution
This is a dew-pressure calculation. Antoine’s constants are (% P in kPa and t
in °C)

A = [13.8858, 14.0045]

B = [2788.51, 3279.47]

C = [220.79, 213.201]

T and the vapor mole fractions are introduced:

T = 100

Y = [0.5,1- 0.5]

Psat = exp [A - B/(T + C)]

= 180.0377 34.2488

The total pressure and the liquid mole fraction are calculated:

P = 1/sum (y./Psat )

x = P*y./Psat

P = 57.5498
x = 0.1598 0.8402

Example 4.3

[Numerical Solution of Linear equations using MATLAB®]

Case of distillation column: (solution of n algebraic equations in n unknowns)
A stream containing 35.0 wt.% benzene (B), 50.0% toluene (T), and the balance
xylene (X) is fed to a distillation column. The overhead product from the column
contains 67.3 wt.% benzene and 30.6% toluene. The bottoms product is fed to a
second column. The overhead product from the second column contains 5.9 wt.%
benzene and 92.6% toluene. Of the toluene fed to the process, 10.0% is recovered
in the bottoms product from the second column, and 90.0% of the xylene fed to
the process is recovered in the same stream.
The Approach to Solve Problems by Computers 55

35 kg B

Column 1

Column 2
n1 n5
50 kg T
0.673 kg B/kg 0.059 kg B/kg
15 kg X
0.306 kg T/kg 0.926 kg T/kg
0.021 kg X/kg 0.015 kg X/kg

n6 kg B
n2 kg B n7 kg T: 10% of T in Column 1
n3 kg T n8 kg X: 90% of X in Column 1
n4 kg X

Column 1 Balances

B: 35.0 = 0.673n1+ n2 (4.3.1)

T: 50.0 = 0.306n1+ n3 (4.3.2)

X: 15.0 = 0.021n1+ n4 (4.3.3)

Column 2 Balances

B: n2 = 0.059n5 + n6 (4.3.4)

T: n3 = 0.926n5 + n7 (4.3.5)

X: n4 = 0.015n5 + n8 (4.3.6)

10% T recovery: n7 = 0.100(50.0) = 5.00 (4.3.7)

93.3% X recovery: n8 = 0.933(15.0) = 14.0 (4.3.8)

A solver tool can be used to solve the MATLAB equations simultaneously.

[n1 n2 n3 n4 n5 n6 n7 n8] = solve(‘35 = 0.673*n1 + n2’,‘50 =
0.306*n2 + n3’,‘15 = 0.021*n1 + n4’,‘n2 = 0.059*n5 + n6’,‘n3 =
0.926*n5 + n7’,‘n4 = 0.015*n5 + n8’,‘n7 = 5’,’n8 = 14’)

Example 4.4

Calculate the temperature and composition of a vapor in equilibrium with a liquid

that is 40.0 mole% benzene, 60.0 mole% toluene at 1 atm. Is the calculated tem-
perature a bubble-point or dew-point temperature?
Solution
Raoult’s law

P = x Ap*A (Tbp ) + xBpB* (Tbp ) + 

56 Chemical Engineering Primer with Computer Applications

Let A = benzene and B = toluene

f(Tbp ) = 0.400p * (Tbp ) + 0.600p * (Tbp ) - 760 mm Hg = 0

The solution procedure is to choose a temperature, evaluate PA* and PB* for that tem-
perature from the Antoine equation, evaluate f(Tbp) from the earlier equation, and
repeat the calculations until a temperature is found for which f(Tbp) is sufficiently
close to 0.
Solve using initial guess (100°C):

1203.5311 1346.773
6.89272- 6.95805-
0.40 × 10 T + 219.888 + 0.6 × 10 T + 219.693 - 760 = 0

 T = fzero(@(T)040*10^89,272 - 12035
, ,311/(T+219,888))

+06*10^95,805  1,346,773/(T+219,693))  760,100)

T = 95.1460

 pA = 040*10^89,272  12035
, ,311/(T+219,888))

pA = 472.5616

 pB = 06*10^95,805  1,346,773/(T+219,693))

pB = 287.4384

 yA = pA/760

yA = 0.6218

 yb = pB/760

yb = 0.3782

The dew-point pressure, which relates to condensation brought about by increas-

ing system pressure at constant temperature, can be determined by solving the
following equation for P:

y APV yBP
+ + = 1
p*A (Tdp ) pB* (Tdp )

0.1* 760 0.1* 760

1203.5311
+ 1346.773
-1= 0
6.89272 - 6.95805 -
10 T + 219.888 10 T+ 219.693
The Approach to Solve Problems by Computers 57

Solve using initial guess:

Tdp = fzero(@(T)(01*760)/10^89272  12035311/(T+219888))

+(01*760)/10^95805  1346773/(T+219693))  1,50)

Tdp = 52.4354 final answer

Example 4.5

For the mixer shown in the following, write a code to find the values of streams
A, B, and C.

W = 100 kg/h
100% benzene

A=? B=?
50% xylene 30% xylene
20% toluene 30% toluene
30% benzene 40% benzene
C=?
40% xylene
20% toluene
40% benzene

Solution
By making a component-material balance on each component within the mixer,
you can reach to a system of three equations that can be solved by using the com-
mand to find the unknowns A, B, and C.
Type the following command:
[A,B,C] = solve(‘.5* A + .3*B = .4*C’, ‘.2*A + .3*B = .2*C’,‘.3*A +
.4*B + 100 = .4*C’). The results will be the following:

A = 600.
B = 200.
C = 900.

Type the same command by entering w = 100 as the fourth equation:

?[A,B,C,W] = solve(‘.5*A + .3*B = .4*C’,’.2*A + .3*B =

.2*C’,’.3*A + .4*B + W = .4*C’,’W = 100’)

The results will be the following:

A = 600.
B = 200.
C = 900.
W = 100.
58 Chemical Engineering Primer with Computer Applications

Example 4.6

For the following distillation column, calculate the values of F1, F3, and F4.

F3 = ?

50% A
F1 = ? 30% B

20% A 20% D

30% B
50% D

F2 = 500
50% A
50% B
F4 = ?

20% A
40% B
40% D

F1,F3,F4] = solve(‘.2*F1 + 250 = .5*F3 + .2*F4’,’.3*F1 + 250 =

.3*F3 + .4*F4’,’.
5*F1 = .2*F3 + .4*F4’)F1 = 1000
F3 = 500
F4 = 1000

Example 4.7: Flash Distillation (Separation)

For the vapor liquid separater shown in the figure, write a program to calculate the values of
XA, XB, YA, YB, L, and V
If you know: V=?
YA = ?
XA + XB = 1
YA + YB = 1 YB = ? F = 100 kg/h
Vapor
YA = KA*XA = 2XA 40% A
YB = KB*XB = 2XB
Liquid 60% B
L=?
XA = ?
XB = ?
Solution:
A=[1,1,0,0;0,0,1,1;–2,0,1,0;0,–.5,0,1];
B=[1;1;0;0]; X=A\B;
xa=X(1),xb=X(2),ya=X(3),yb=X(4)
a=[xa,ya;xb,yb];
b=[.4*100;.6*100];
x=a\b;
L=x(1),V=x(2)
The Approach to Solve Problems by Computers 59

Gives the results

xa =
0.3333xb =
0.6667 ya =
0.6667 yb = 0.3333
L = 80
V = 20.0000

Example 4.8: Txy Diagram for Ethanol–Water System

Plot the Txy diagram for ethanol–water system, knowing the vapor pressure for
three components is calculated by

Ethanol Poe = exp(18.5242–3578.91/(T–50.5))

Water Pow = exp(18.3036–3816.44/(T–46.13))
Where Vapor y,T
Ki = Poi/Pt
Pt = 760
yi = Ki×xi Liquid x,T
At bubble point ∑yi = ∑Ki×xi = 1

Solution:
Xe = 0:.1:1;
Xw = 1–Xe;
for m = 1:11
for T = 273.15:.01:450;

Txy diagram of ethanol/water system

380

375

370
Temperature (K)

365

360

355

350

345

340
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y for ethanol
60 Chemical Engineering Primer with Computer Applications

Example 4.9: Txy Diagram for Benzene–Toluene Mixture Using Excel

The main five equations relating the seven variables x, T, p*a , p*b , pa, pb, and y are
given in the following.
Equations 4.9.1 and 4.9.2 are the Antoine equations for benzene (a) and toluene
(b), respectively. These give the vapor pressure pi* in mm Hg of the pure liquids,
a or b versus temperature T in °C. Here, xa is the mole fraction of benzene in the
liquid, ya is its mole fraction in the vapor, and pi is the partial pressure of i for a or
b. Equations 4.9.3 and 4.9.4 come from assuming an ideal liquid mixture, which is
approximately true for benzene and toluene.
Find
The goal is to create a Txy phase diagram for mixtures of benzene and toluene,
where T is the temperature, x is the mole fraction of benzene in the liquid, and y
is the mole fraction of benzene in the vapor. A horizontal line drawn for a given T
gives the compositions of liquid and vapor in equilibrium at that T. Such diagrams
are very useful for distillation calculations
Approach: Using these equations, you will create a Txy graph for benzene–toluene
mixtures at 1 atm. This graph will show the mole fraction ya of benzene in the
vapor corresponding to equilibrium with liquid of mole fraction xa at temperature
T required to give a total pressure of 760 mm Hg:

1090
log10 p*a = 6.814 - (4.9.1)
197.1+ T

1457
log10 p*b = 7.136 - (4.9.2)
231.8 + T

pa = xp*a (4.9.3)

pb = (1- x)p*b (4.9.4)

pa
y= (4.9.5)
pa + pb

Proposed Procedure

1. Create an Excel spreadsheet giving T and y versus x for P = 760 Torr

(mm Hg), and then execute the following steps:
a. Enter the values for the Antoine constants from Equations 4.9.1 and
4.9.2.
b. In column A enter values for x from 0 to 1 by increments of 0.1.
c. Leave column B blank for values of T.
d. In column C calculate p*a using the Antoine equation, the constants
for benzene, and the temperature in column B.
The Approach to Solve Problems by Computers 61

e. In column D calculate p*b using the Antoine equation, the constants

for toluene, and the temperature in column B.
f. In column E calculate P = pa + pb using columns C and D and
Equations 4.9.3 and 4.9.4.
g. In column F use Equation 4.9.5 to calculate the values of y.
h. Use Goal Seek row-by-row to calculate T required to give P =
760 mm Hg. This will automatically fill in the correct values in all
columns.
2. Use the results in the spreadsheet to create a graph, with x and y on the
horizontal (X) axis and T on the vertical (Y) axis.
3. Format the graph.

Results will be as shown in Figure 4.4:

FIGURE 4.4 Calculation of the equilibrium data for Benzene/Toluene mixture using Excel.
(Courtesy of Clarkson University, Engineering spreadsheets Using Excel II. Goalseek and
Graphing, Potsdam, NY, n.d., http://clarkson.edu/~wwilcox/ES100/xl-tut2.pdf, accessed
October 14, 2014.)
62 Chemical Engineering Primer with Computer Applications

115
Calculated Txy diagram for benzene and toluene at 1 atm
110

105
Vapor
Temperature (°C)

100
Vapor + liquid
95

90 Liquid

85

80

75
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Mole fraction benzene

Example 4.10

Given

i. The vapor pressure data measured at a pressure of 101.32 kPa as shown

in Table 4.1
ii. Using Raoult’s law

Find: Calculate the vapor and liquid compositions in equilibrium (in mole frac-
tions, y and x) for the benzene–toluene system, and plot the Txy diagram.

TABLE 4.1
Temperature–Vapor Pressure Data for Benzene–Toluene
at 101.32 kPa
Vapor Pressure
Temperature Benzene Toluene
K °C kPa mm Hg kPa mm Hg
353.3 80.1 101.32 760 — —
358.2 85.0 116.9 877 46.0 345
363.2 90.0 135.5 1016 54.0 405
368.2 95.0 155.7 1168 63.3 475
373.2 100.0 179.2 1344 74.3 557
378.2 105.0 204.2 1532 86.0 645
383.3 110.6 240.0 1800 101.32 760
The Approach to Solve Problems by Computers 63

Solution
Step 1
Write Raoult’s law for a binary mixture of A and B:

PA = PA*x A ; PB = PB*xB = PB* (1- x A )

The total pressure PT = PA + PB

Replacing for the partial pressures and rearranging, we have

PT = PA*x A + PB* (1- x A )

PT = (PA* - PB* )x A + PB*

Rearranging, we have the expression for xA

PT - PB*
xA =
PA* - PB*

Since PA*x A = y APT , we have the expression for yA

æ P* ö
y A = ç A ÷ xA
ç PT ÷
è ø

Step 2
The vapor-liquid-equilibrium (VLE) data can be calculated at each temperature by
substituting for total pressure (101.32 kPa) and the appropriate vapor pressures.
For example, at 85.0°C,
101.32 - 46.0
xA = = 0.7803
116.9 - 46.0
æ 116.9 ö
yA = ç ÷ (0.7803)
è 101.32 ø

Step 3
Repeating for other temperatures using Excel, the following results are obtained

Mole Fraction of Benzene Mole Fraction of Benzene

Temperature (°C) in Liquid (x) in Vapor (y)
80.1 1.000 1.000
85.0 0.780 0.900
90.0 0.581 0.777
95.0 0.411 0.632
100.0 0.258 0.456
105.0 0.130 0.261
110.6 0.000 0.000

Source: Chemical Eng. Computing Lab. Manual, KFUPM, Dhahran, Saudi

Arabia, September 2001.
64 Chemical Engineering Primer with Computer Applications

110

105

y
Temperature (°C)
100

95 x

90

85

80
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction of benzene in liquid (x) and vapor (y)
Txy diagram for benzene-toluene system at 1 atm

Example 4.11

Plot Pxy diagram for the binary system of acetonitrile (1)/nitromethane (2). Vapor
pressures for the pure species are given by the following equations:
For acetonitrile (1), P1o = exp(14.2724 - 2945.47/(T + 224)).
For nitromethane (2), P2o = exp(14.2043 - 2972.64/(T + 209)),
in which
T = 75°C
P1 and P2 in kPa

Pio
Ki =
Pt

At bubble point, å yi = å Ki ´ xi = 1
Solution
Write the following code:

X1 = 0:.1:1;
X2 = 1−X1;
T = 75;
P1 = exp(14.2724 - 2945.47/(T + 224));% Vapor pressure of
acetonitrile
P2 = exp(14.2043 - 2972.64/(T + 209));% Vapor pressure of
nitromethane for m = 1:11
for Pt = .1:.01:120;
K1 = P1/Pt; % acetonitrile
K2 = P2/Pt; % nitromethane
The Approach to Solve Problems by Computers 65

sum = K1*X1(m) + K2*X2(m);

if sum<1
break
end
end
Press(m) = Pt;
Y1(m) = K1*X1(m);
end
plot(X1,Press,’k− +‘,Y1,Press,’k−*‘)
axis ([0 1 20 100])
xlabel(‘x,y for acetonitrile’)
ylabel(‘Pt (kpa)’)
title(‘Pxy diagram of system acetonitrile/nitromethane
system’)

Pxy diagram of system acetonitrile/nitromethane system

100

90

80

70
Pt (kPa)

60

50

40

30

20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x, y for acetonitrile

REFERENCES
Clarkson University, n.d., Engineering Spreadsheets Using Excel II. Goalseek and Graphing,
Potsdam, NY. http://clarkson.edu/~wwilcox/ES100/xl-tut2.pdf (accessed October 14,
2014).
Planck, M. Treatise on Thermodynamics, A. Ogg (Trans.), London: Longmans, Green & Co.
https://archive.org/details/treatiseonthermo00planrich, 1903.
Towler, G. and Sinnott, R.K. Chemical Engineering Design: Principles, Practice and
Economics of Plant and Process Design, New York: Elsevier, 2013.
Section III
Backbone Materials

As stated in the “Introduction”, a handy collective source of basic principles and

techniques in chemical engineering organized in a summary manner is a prime fea-
ture of this text. Having presented—in Sections I and II—the basic concepts and
principles as introduction to calculations and described how to device and evaluate
numerical techniques to solve problems through standard algorithm, we turn next to
Section III.
Section III consists of Chapters 5 through 10. They represent what may be named
“The Backbone Materials of Chemical Engineering.” Each chapter in this section,
except Chapter 10, will encompass two sections: one includes the theoretical prin-
ciples in a condensed format, the other presents a set of numerically solved problems
using interactive numerical software packages (Excel, MATLAB®). This way, the
dual themes of presenting the fundamentals followed by computer applications are
realized. Application problems for Section III are found in Appendix A.
Chapter 10 stands unique in its function. It includes six case studies covering dif-
ferent topics.
 5 Fluid Flow and
Transport of Fluids

Fluid
Fluid Basic definitions
statics
mechanics is of fluids
classified Fluid
into: dynamic
1. Compressible and
noncompressible.
2. Pressure concept
Classification of
3. Newton’s second law
fluid flow states that: ∑ F = m . a
4. Poise is viscosity unit
5. Kinematic viscosity:
v = µ/ρ , Stoke is the
unit
Ideal and Steady and Uniform and Laminar and
real fluid unsteady nonuniform turbulent
flow state flow

Important 1. What is Velocity gradient or rate of shear stress (du/dy)?

tips
2. What is meant by a shear stress (τ)?

3. Absolute pressure = gauge pressure (taken with the proper sign) + atmospheric pressure.
4. Fluid statics is concerned with the static properties and behavior of fluids

Bernoulli’s equation

Bernoulli’s equation is a special case of the general energy equation

(mechanical energy balance)

Piping and pumps

1. The diameter of a pipe is a function of the flow rate of the fluid: D = f (Q), while
2. The thickness of a pipe (t) is a function of the working pressure inside the pipe:
t = f (p)

5.1 INTRODUCTION
Before a formal definition of fluid is given, it is known that the three common states
of matter are solid, liquid, and gas. A fluid is either a liquid or a gas. A fluid is defined
as a substance that deforms continuously under the application of a shear stress.
The definition of a stress would illustrate some basic principles. A stress is defined
as a force per unit area, acting on an infinitesimal surface element. Stresses have

69
70 Chemical Engineering Primer with Computer Applications

both magnitude (force per unit area) and direction, and the direction is relative to the
surface on which the stress acts. Stresses are classified into two main types: normal
stresses and tangential stresses. Pressure is an example of a normal stress and acts
inward, toward the surface, and perpendicular to the surface; on the other hand, a
shear stress is an example of a tangential stress, that is, it acts along the surface,
parallel to the surface. Friction due to fluid viscosity is the primary source of shear
stresses in a fluid.
Fluid mechanics has two branches, as shown next:

Fluid mechanics

Fluid Fluid
statics dynamics

Fluid statics treats fluid in the equilibrium state (no motion), while fluid dynam-
ics treats fluids when portion of the fluid are in motion (concerned with the relation
between the fluid velocity and the forces acting on it).

5.2 DEFINITIONS AND TERMINOLOGY IN FLUID MECHANICS

5.2.1 compressIBle and noncompressIBle fluIds
A compressible fluid is identified by a fluid density sensitive to any change in tem-
perature or pressure (including gases and vapors). On the other hand, if no change
or little change in density occurs with change of pressure or temperature, the fluid is
termed incompressible fluid (including liquids).

5.2.2 pressure concept

The basic property of a static fluid is pressure. Pressure is familiar as a surface force
exerted by a fluid against the walls of its container.

5.2.3 forces actIng on a fluId

Any fluid may be subjected to three types of forces:

1. Gravity force (body force: acts without physical contact)

2. Pressure force (surface force: requires physical contact for transmission)
3. Shear force (appears in case of dynamic fluids) (surface force)

Newton’s second law states that

åF = m ×a
Fluid Flow and Transport of Fluids 71

y τ = F/A u

F du
=τ=η
du/dy A dy

FIGURE 5.1 Representation of viscosity.

This law is applied for fluid statics and fluid dynamics, while for fluid statics,

å F = 0.0
5.2.4 nature of fluIds
As explained earlier, a fluid undergoes continuous deformation when subjected to a
shear stress. The resistance offered by a real fluid to such deformation is called its
consistency. Now, if the static pressure and temperature are fixed, the consistency of
the fluid is constant. This is defined as a Newtonian fluid (simple fluids and gases), and
consistency is called viscosity. If, however, consistency is a function of shear stress as
well as of temperature, the fluid is called nonnewtonian fluid (see Figure 5.1).
The unit of viscosity (i.e., absolute viscosity) in the cgs system is defined as the poise
(p) = 1 g/(cm)(s). Viscosities are usually tabulated in centipoises: 1 (cp) = 0.01 poise.
Kinematic viscosity of a fluid of density  lb/cu × ft and viscosity µ lb/(ft)(s) is given
by

m 2
v= ft /s
r

The cgs unit of kinematic viscosity is known as stoke:

1 stoke = 1 cm 2 /s

5.3 CLASSIFICATION OF FLUID FLOW

Fluid flow is classified into:

Ideal and real Steady and Uniform and Laminar and

fluid flow unsteady state nonuniform turbulent
(a) (b) (c) (d)
72 Chemical Engineering Primer with Computer Applications

5.3.1 Ideal fluId flow

This flow is characterized by the following:

• There is no friction (viscosity is zero), that is, there is no dissipation of

mechanical energy into heat.
• All particles flow in parallel lines and equal velocities (no velocity gradient).
• There is no formation of eddies or circulation within the stream.

This type of flow is also called potential flow or irrotational flow. This can exist at a
distance not far from a solid boundary (outside the boundary layer).

5.3.2 real fluId flow

This type of flow is characterized by the following:

• There is the presence of friction.

• There is a velocity gradient.

This type exists inside the boundary layer where the fluid is affected by the presence
of solid boundaries.

5.3.3 steady and unsteady state flow

• Steady state: In this type of flow, the conditions are independent of time
(invariant with time).
• Unsteady state: The conditions are dependent to time (change with time).

5.3.4 unIform and nonunIform flow

In the uniform type of flow, the conditions (velocity) are independent on position
(space coordinate), while the conditions for nonuniform flow are position dependent.
It is to be noted that uniform flow is ideal flow and nonuniform flow is real flow.

5.3.5 lamInar flow

This type of flow exists at low velocities and assumes that the fluid adjacent layers
slide past one another like playing cards. This type of flow is characterized by the
fact that there is no lateral mixing and no crosscurrent or eddies, and the velocity
gradient is high.

5.3.6 turBulent flow

Turbulent flow exists at high velocities and is characterized by the fact that there is
mixing and crosscurrents, and the velocity gradient is lower than that of laminar
flow.
Fluid Flow and Transport of Fluids 73

5.4 PARAMETERS IN LAMINAR FLOW

Two important parameters are identified in laminar flow as explained next.

5.4.1 velocIty gradIent or rate of shear stress (du/dy)

For a steady-state 1D flow of an incompressible fluid over a solid plane surface, the
picture is as presented in Figures 5.2 and 5.3. Now, by plotting the velocity versus
distance (in y direction), we observe the following:

• The velocity is zero at the wall.

Velocity profile
Inviscid
U(x)
region

Viscous
region
u(x,y)
Boundary
layer
thickness
Viscosity 3
velocity gradient =
wall shear stress

No-slip at a
solid surface

FIGURE 5.2 Velocity gradient.

Velocity far enough away

from the plate is the u∞ Free stream
δ (x)
free stream velocity
u∞
u
y Velocity
δ τ boundary
layer
τ

x
Velocity of the fluid is
zero at the plate

FIGURE 5.3 Change of velocity profile with x.

74 Chemical Engineering Primer with Computer Applications

• As the distance increases, the velocity increases (with a decreasing rate)

until the maximum velocity is reached after which the fluid will be not
affected by the wall.
• The fluid velocity at which the fluid is not affected by the wall is called the
free stream velocity.

By plotting (y) versus (du/dy), the figure shows that the velocity gradient (rate of
shear stress) is maximum at the wall and decreases as the distance increases to reach
the minimum value at the free stream velocity.

Rate of shear stress (du/dy)

5.4.2 shear stress (τ)

Wherever there is a velocity gradient, a shear force must exist. The shear force acts
parallel to the plane of the shear. The ratio between the shear force to the shear area
is called the shear stress.

5.5 FLUID STATICS

Fluid statics is concerned with the static properties and behavior of fluids. Two cases
are known:

1. Hydrostatics, the case dealing with liquids

2. Pneumatics, the case dealing with gases

A body of liquid in a static equilibrium is being acted upon only by compressive

forces. The intensity of this force is known as the static pressure. It is expressed in
terms of

• Pound force per square inch

• Dyne per square meter

5.5.1 gauge pressure and aBsolute pressure

The difference between a given fluid pressure and the atmospheric pressure is
known as the gauge pressure. Reading of pressure gauges is normally positive
Fluid Flow and Transport of Fluids 75

gauge pressures. Absolute pressure, on the other hand, is the true total pressure
and is given by

Absolute pressure = Gauge pressure (taken with the proper sign)

+ atmospheric pressure

The term static head generally means the pressure of a fluid exerted by the head of a
fluid above the point in question.
Newton’s law, which is given by the equation force = mass × acceleration, is used
to determine the pressure as shown.
For constant density fluids, the static head is given by

hrg
ph =
gc

where
h is the head of liquid above the point, ft
ρ is the liquid density, lb/cu · ft
g is the local acceleration due to gravity, ft/s2
gc is the dimensional constant, 32.17 (lb)(ft)/(lb · force)(s2)

5.6 OVERALL ENERGY BALANCE EQUATION

5.6.1 IntroductIon
In order to write an energy balance, we need to know what kinds of energy can enter
or leave a system. Energy is often categorized as

• Kinetic energy (KE)

• Potential energy (PE)
• Internal energy (U)

The total amount of energy entering the system is the sum of all of the different types
entering the system. Energy may be transferred between a system and a boundary
by two modes:

1. Heat: Q
2. Work: W

5.6.2 general energy Balance equatIon

Now, assume a system having a total energy E. If Q is added to it from the surround-
ing, then as a result, W, is done by the system, and the output streams are leaving. Then
Energy available in output streams = Energy available in input streams
that is,

DU + DK.E. + DP.E. = Q - WT (first law of thermodynamics)

76 Chemical Engineering Primer with Computer Applications

or

DU + DK.E. + DP.E. + DPV = Q - Ws (5.1)

where WT is the sum of Ws + ΔPV. This term, ΔPV, is called the flow work that is the
work done on the fluid at the inlet minus work done by the fluid at the outlet.
If we define

DU + DPV = DH ,

enthalpy changes and the following equation is obtained:

DH + DK.E. + DP.E. = Q - Ws = DE = Change in total energy of a system (5.2)

5.6.3 specIal cases

5.6.4 mechanIcal energy Balance
Replacing V by 1/ρ in Equation 5.1, we get

DP
DK.E. + DP.E. + + (DU - Q) = -Ws (5.3)
r

This term, ΔU – Q, represents the friction losses in our system. It means that this
energy appears as friction losses, F. Equation 5.3 can be rewritten as

DP
DK.E. + DP.E. + + F + Ws = 0 (5.4)
r

Closed (batch): Flow, general Flow, general

∆E = Q–Ws ∆H = Q–Ws ∆H = Q

∆H = 0, ∆K.E. = 0, ∆P.E. = 0 where, ∆K.E. = ∆P.E. = 0 Ws = 0

These are the cases that apply for most

chemical processes, such as reactors,
distillation units, and others

This equation is the basis of heat

balance for many processes
Fluid Flow and Transport of Fluids 77

5.6.5 Bernoulli’s equation

Bernoulli’s equation is a special case of the general energy equation (mechanical
energy balance) that is probably the most widely used tool for solving fluid flow
problems. It provides an easy way to relate the elevation head, velocity head, and
pressure head of a fluid.
Bernoulli’s equation results from the application of the general energy equation
and the first law of thermodynamics to a steady-flow system.
The general form of the energy balance equation is

å(all energies in ) = å (all energies out) + å (energy stored in system)

å Ein = å Eout + å Estorage

Consider a steady-flow system in which no work is done on or by the fluid, no heat is

transferred to or from the fluid, and no change occurs in the internal energy (i.e., no
temperature change) of the fluid. Under these conditions, the general energy equation
is simplified to

(PE + KE + PV)1 = (PE + KE + PV)2

W Q

Vin2 g V2out g
min uin+ Pin vin+ + Z mout uout + Pout vout + + Z
2gc gc in 2gc gc out

System boundary

Substitution for each term

p1 g u2 p g u2
+ Z1 + 1 = 2 + Z 2 + 2
r g c 2g c r g c 2g c

This equation is the simplified form of Bernoulli’s equation and is used for friction-
less flow; no work is applied on the fluid and no heat is added or lost from the fluid.
Each term in Bernoulli’s equation represents a form of energy possessed by a
moving fluid (potential-, kinetic-, and pressure-related energies). In essence, the
equation physically represents a balance of the KE, PE, and PV energies so that if
one form of energy increases, one or more of the others will decrease to compensate
and vice versa. It is to be noted that each term of Bernoulli’s equation has a unit of
energy per unit mass (J/kg or lbf · ft/lbm).
78 Chemical Engineering Primer with Computer Applications

5.6.6 Head Form oF Bernoulli’s equation

Multiplying all terms in Bernoulli’s equation by the factor gc/g results in the form of
Bernoulli’s equation shown
p1 gc u2 p g u2
+ Z1 + 1 = 2 c + Z 2 + 2
r g 2g r g 2g

The units for all the different forms of energy in this equation are measured in units
of distance; these terms are sometimes referred to as heads (pressure head, velocity
head, and elevation head). Each of the energies possessed by a fluid can be expressed
in terms of head.
It has been established that the elevation head represents the PE of a fluid due to
its elevation above a reference level. The velocity head represents the KE of the fluid.
It is the height in feet that a flowing fluid would rise in a column if all of its KE were
converted to PE. The pressure head represents the flow energy of a column of fluid
whose weight is equivalent to the pressure of the fluid.
The sum of the elevation head, velocity head, and pressure head of a fluid is called
the total head.
Thus, Bernoulli’s equation states that the total head of the fluid is constant.
Bernoulli’s equation can be modified to take into account the friction losses in the
fluid flow to be in the form:
V2 V2
åF
p1 g p g
+ Z1 + 1 = 2 + Z 2 + 2 +
r gc 2a1gc r g c 2a 2 g c

where F is the friction loss in the piping system between point 1 and point 2 includ-
ing both the skin and form friction.
If the flow line contains a device that adds work to the fluid, Bernoulli’s equation
will take the form
V2 V2
åF
p1 g p g
+ Z1 + 1 + hW = 2 + Z 2 + 2 +
r gc 2a1gc r g c 2a 2 g c

where
W is the mechanical work done by the pump per unit mass of fluid
η is the pump efficiency
W - friction losses in the pump
h=
W

5.6.7 Pressure droP and Friction losses

The Fanning friction factor is a dimensionless number used in fluid flow calcula-
tions. It is a common parameter used in laminar and especially in turbulent flow.
It is defined as the drag force per wetted unit surface area (i.e., shear stress), divided
by the product of density times velocity head or ½ρυ2. The force is Δpf, times the
cross-sectional area π R2 and the wetted surface area 2πR∆L.
 Fluid Flow and Transport of Fluids 79

The relation between the Δpf due to friction and f is given as follows:
éæ DL ö æ u2 ö ù
Dpf = 4fr êç ÷ ç ÷ú
êëè D ø è 2 ø úû

or

Dpf æ DL ö æ u2 ö
Ff = = 4f ç ÷ç ÷
r è D øè 2 ø

For laminar flow, the friction factor is given by

16
f=
N Re

This relationship holds up to a Reynolds (Re) number of 2100. Beyond that and for
turbulent flow and for design purposes, Moody chart, shown in Figure 5.4, is used to
predict the value of f and, hence, the frictional pressure drop of round pipes.

Moody diagram
0.1
0.09
0.08 Transition region
0.07 0.05
0.04
0.06 0.03
0.05 0.02
0.015

d
Relative pipe roughness ε
0.04 0.01
Friction factor

0.03 0.005

Laminar flow 0.002

0.02 64 0.001
Re 5 × 10–4
0.015
2 × 10–4
10–4
Complete turbulence 5 × 10–5
0.01
2d 10–5 –6
Friction factor = 2l
∆P 5 × 10
ρV Smooth pipe 10–6
3
10 104 105 106 107 108
ρV d
Reynolds number, Re =
μ

Material ε (mm)
Concrete, coarse 0.25
Concrete, new smooth 0.025
Drawn rubing 0.0025
Glass, plastic, perspex 0.0025
Iron, cast 0.15
Sewers, old 3.0
Steel, mortar lined 0.1
Steel, rusted 0.5
Steel, structural or forged 0.025
Water mains, old 1.0

FIGURE 5.4 Friction factor for fluids inside pipes.

80 Chemical Engineering Primer with Computer Applications

5.7 PIPING AND PUMPS

5.7.1 introduction
Pipelines along with pumps are needed as an efficient means of transporting fluids,
in general, such as natural gas and other important fossil fuels, speedily, safely, and
smoothly. Pipelines need to be constantly and reliably operated and monitored in order to
ensure maximum operating efficiency, safe transportation, and minimal downtimes and
to maintain environmental and quality standards. Powerful pumps, on the other hand,
are needed for transport of fluids, to overcome frictional losses and changes in elevation.
In general, two types of fluids are encountered: noncompressible fluids and com-
pressible fluids.

5.7.2 PiPing
5.7.2.1 Sizing of Pipelines
Choosing a pipeline size and determining wall thickness represent a major target in the
design of piping system. In this respect, one should be aware of two fundamental concepts

1. The diameter of a pipe is a function of the flow rate of the fluid: D = f(Q)
2. The thickness of a pipe is a function of the working pressure inside the pipe:
t = f(p)

By sizing, we mean to determine the pipe diameter first. An engineer in charge must
specify the diameter of the pipe that will be used in a given piping system. Normally,
the economic factor must be considered in determining the optimum pipe diameter.
To calculate the pipe diameter for noncompressible fluids, one can apply the fol-
lowing well-known equation:

Q = u × A(cross - sectional area of pipe)

= u[ p/4]d 2

Pipe diameter, d, is readily calculated from this equation for a specified flow rate Q
(bbl/h) and for an assumed fluid velocity u (ft/s).

5.7.2.2 Economic Balance in Piping and Optimum Pipe Diameter

When pumping of a specified quantity of fluid over a given distance, two alternatives
exist and a decision has to be made

1. Whether to use a large-diameter pipe with a small pressure drop

2. Whether to use a smaller-diameter pipe with a greater pressure drop

The first alternative involves a higher capital cost with lower running costs; the sec-
ond involves a lower capital cost with higher running costs specifically because of
the need for more pumps.
So it is necessary to arrive at an economic balance between the two alternatives.
Unfortunately, there are no hard and fast rules or formulas to use; every case is different.
Fluid Flow and Transport of Fluids 81

Total costs
Annual cost, dollars/(year)

Annual fixed charges

Annual variable
cost for pumping

Optimum economic
pipe diameter

o Pipe diameter

FIGURE 5.5 Optimum economic pipe diameter.

The costs of actual pumping equipment undoubtedly must be considered, but the area
in which the pipes will run is also important. For instance, to obtain the same pumping
effort in the desert as opposed to a populated area could involve much higher costs in the
form of providing outside services and even creating a small, self-contained township.
In the flow of oil in pipes, the fixed charges are the cost of the pipe, all fittings,
and installation. All these fixed costs can be related to pipe size to give an approxi-
mate mathematical expression for the sum of the fixed charges.
In the same way, direct costs, or variable costs, comprising mostly the costs of
power for pressure drop plus costs of minor items such as repairs and maintenance,
can be related to pipe size. For a given flow, the power cost decreases as the pipe size
increases. Thus, direct costs decrease with pipe size. And total costs, which include
fixed charges, reach a minimum at some optimum pipe size. The ultimate solution lead-
ing to the optimum economic diameter is found from the graph shown in Figure 5.5.

5.7.2.3 Stepwise Procedure to Calculate the Wall Thickness

• Determine D i (as shown in 5.7.2.2), guided by the allowable pressure drop
in a pipeline (ΔP).
• Select a material of construction; S (tensile strength) is determined.
• Knowing our operating pressure, Schedule No = 1000 P/S is calculated.
• If severe corrosion is anticipated in your pipe system, choose a larger sched-
ule no.
82 Chemical Engineering Primer with Computer Applications

• Pick up a nominal pipe size with the specified schedule no. that gives Di for
our flow equal or slightly greater than Di obtained before.
• As a final check, use the following equation to calculate the safe working
pressure:
Schedule No = 1000 P/S = 2000(tm /Dav); solving this relationship to obtain

ét ù
Ps = 2Ss ê m ú
ë Dav û

where
P is the operating pressure
Ps is the safe working pressure
Ss is the safe working fiber stress
S is the tensile strength, the greatest longitudinal stress a material can
bear without tearing apart
tm is the minimum thickness of pipe
Dav is the average diameter of Di and Do

There are many factors that affect the pipe wall thickness, which include

• The maximum and working pressures

• Maximum and working temperatures
• Chemical properties of the fluid
• The fluid velocity
• The pipe material and grade
• The safety factor or code design application

5.7.2.4 Relationship between the Pipe Diameter and the Pressure Drops
Two scenarios could be followed: either to assume a value for the velocity u and cal-
culate ΔP or to consider an allowable value for the pressure drop ΔP and calculate
the corresponding u.
The first scenario is illustrated by the following block diagram:

Calculate u and Calculate f Calculate ∆P =

Given: Q (ft3)/m and D (ft) [4/Digc][1/2ℓu2f]
Calculate: u and check ∆P Re no = ℓuDi/µ f is F(Re)

Lower (∆P)cal by Check (∆P)calc

Repeat steps increasing Di (∆P)cal is ≥ (∆P)spec
against (∆P)spec ?
above (to decrease u)

(∆P)cal is ≤ (∆P)spec

Solution
Fluid Flow and Transport of Fluids 83

To determine the fluid velocity in a pipe, the rule-of-thumb economic velocity for
turbulent flow is used, as given next:

Type of Fluid Reasonable Assumed u (ft/s)

Water or fluid similar to water 3–10
Low-pressure steam (25 psig) 50–100
High-pressure steam (>100 psig) 100–200

Economies of scale is the major element in pipeline economies. From a theoreti-

cal point of view, doubling the pipeline diameter will tend to increase the amount
delivered by more than fourfold in a given period of time—other factors remaining
constant. This implies that total cost might double, while the cost per unit delivered
would decline. In planning a pipeline system, crude oil moves at a speed of 5 km/h
via pipeline, roughly a walking speed.
Pipeline capacity is normally defined as the quantity (volume) of oil and gas required
to maintain a full pipeline. The static capacity of a pipeline is usually expressed as
a volume per unit length (e.g., bbl/ft). On the other hand, the fluid volume passing
through a pipeline in a specific time period will depend on the following factors:

• Initial pressure
• Flow characteristics and fluid density
• Ground elevation
• Delivery pressure

5.7.3 PumPs
5.7.3.1 Introduction
A fluid moves through a pipe or a conduit by increasing the pressure of the fluid
using a pump, which supplies the driving force for flow. In doing so, power must be
provided to the pump. There are six basic means that cause the transfer of fluid flow:
gravity, displacement, centrifugal force, electromagnetic force, transfer of momen-
tum, and mechanical impulse. Excluding gravity, centrifugal force is the means most
commonly used today in pumping fluids.
Centrifugal force is applied by using centrifugal pump or compressor, where the
basic function of each is the same. That is to produce KE by the action of centrifugal
force and then converting this KE into potential energy (PE) by efficient reduction of
the velocity of the flowing fluid.
Fluid flow in pipes applying centrifugal devices has in general the following basic
advantages and features:

• Fluid discharge is relatively free from pulsations.

• There is no limitation on throughput capacity of the operating pump.
• Discharge pressure is a function of the fluid density, that is, P = f( f ).
• Efficient performance is provided in a simple way with low first cost.
84 Chemical Engineering Primer with Computer Applications

5.7.3.2 Classification and Types of Pumps

1. Pumps can be classified into three major groups according to the method
they use to move the fluid:
a. Direct lift
b. Displacement
c. Gravity pumps
2. Pumps can also be classified by their method of displacement as
a. Positive displacement pumps
b. Impulse pumps
c. Velocity pumps
d. Gravity pumps
3. Pumps operate by some mechanism
a. Reciprocating
b. Rotary
4. Mechanical pumps may be
a. Submerged in the fluid they are pumping
b. Placed external to the fluid

A concise summary for the comparison between different types of pump is found in
Table 5.1.
Pumps are used for many different applications. Understanding which pump type
one needs for this application is very important. For the oil and gas industry, some
basic features are listed next:

1. Pumps should handle the fluids with low shear and least damage to droplet
sizes causing no emulsions for the effective separation of water from oil.
2. Pumps should be self-priming and experience no gas locking.
3. The requirement of having low net positive suction head is an advantage.
This is advantageous for vessel-emptying applications such as closed-drain
drums or flare knockout drums or any applications encountering high-vapor
pressure liquids.
4. Pumps should handle multiphase fluids.

TABLE 5.1
Comparison between Types of Pumps
Type of Pump Features
Centrifugal Most common; high capacity; discharge lines can be shut off (safe).
Handle liquids with solids.
Reciprocating Low capacity and high head; can handle viscous fluids; used to
discharge bitumen (asphalt) in vacuum distillation columns.
Rotary positive displacement Combination of rotary motion and positive displacement; used in gas
pumps, screw pumps, and metering pumps.
Air displacement Nonmechanical, airlift type; used for acid eggs and jet pumps
Fluid Flow and Transport of Fluids 85

5.7.3.3 How to Select a Pump?

The following guide to pump types should prove to be helpful for better understand-
ing the advantages and specifications for each pump type (Hydraulic Institute, n.d.,
FAO Corporation Document Repository, 2011):

• American Petroleum Institute (API) process pumps: Designed to meet the

610 standard set by the API.
• Boiler feed pumps: Built to control the amount of water that enters a boiler.
They are centrifugal pumps and most are multistage.
• Chemical pumps: Built to handle abrasive and corrosive industrial materi-
als. They can be of either centrifugal or positive displacement type.
• Circulator pumps: Used to circulate fluid through a closed or looped sys-
tem. They are usually centrifugal pumps, but a few use positive displace-
ment technologies.
• Dewatering pumps: A dewatering process involves using a centrifugal
pump (submersible or vertical turbine) to remove water from a construction
site, pond, mine shaft, or any other area.
• Fire pumps: A type of centrifugal pump used for firefighting. They are gen-
erally horizontal split case, end suction, or vertical turbine.
• High-pressure pumps: Used in many applications including water blast,
hydromining, and jet cutting. They can be a wide variety of pump types
including positive displacement pumps, rotary pumps, and reciprocating
pumps or centrifugal pumps.
• Industrial pumps: Used in industrial applications such as slurry, wastewa-
ter, industrial chemicals, oil, and gas. There are dozens of different indus-
trial pumps both in positive displacement and centrifugal pump types.
• Marine pumps: Built to pump seawater. They are often used in large saltwa-
ter tanks to continuously circulated water so it stays fresh.
• Mixed flow pumps: Incorporate the features of both axial flow pumps and
radial flow pumps. Axial flow pumps operate on a vertical plane and radial
flow pumps operate on a horizontal plane to the flow direction of water.
• Mud pumps: Built to transfer heavy sludge or mud. Some larger versions are used
to pressure. They are sometimes used on oil rigs to pressurize and circulate fluid.
• Petrochemical pumps: Made to transfer petroleum products that are often
very viscous and corrosive. They can be magnetic drive pumps, diaphragm
pumps, piston pumps, and others.
• Pneumatic pumps: Use compressed air to pressurize liquid through the pip-
ing system.
• Pressure pumps: Used to create either high or low pressure. They can be
metering pumps and sometimes booster pumps.
• Process pumps: Are many times centrifugal pumps or positive displacement
pumps used in process applications. The type of pump and construction
details varies depending on the application in which these pumps are used.
• Slurry pumps: A heavy-duty pump that is made to handle thick, abrasive
slurries. They are made of durable materials and capable of handling abra-
sive fluids for long periods of time.
86 Chemical Engineering Primer with Computer Applications

• Solar pumps: Powered by the sun. They can be positive displacement pumps
or centrifugal pumps.
• Water pumps: A type of equipment used to move water through a piping
system. They rely upon principles of displacement, gravity, suction, and
vacuums to move water. They can be either positive displacement or cen-
trifugal pumps.
• Well pumps: Designed to draw water to the surface from an underground
water source. Depending on the well depth and configuration, these pumps
can be jet pumps, centrifugal pumps, or submersible pumps.

In conclusion, the final selection of a pump for a particular operation is influenced by

many factors, including the following:

• Pump capacity (size) that is a function of the flow rate to be pumped

• Fluid properties, both physical and chemical
• Operating conditions
• Type of power supply
• Type of flow distribution

5.7.3.4 Calculation of the Horsepower for a Pump

This method is recommended to calculate the horsepower (HP) for a pump as a func-
tion of the flow rate and the total equivalent head or the gauge pressure. It is much
simpler to apply than using the mechanical energy equation:

[H ×  × Q] [P × Q]
HP (hydraulic horsepower) = =
3960 1714

HP(hydraulic)
Brake HP (actual) =
a

where
H is the head in ft
 is the specific gravity
Q is the flow rate (gpm)
P is the gauge pressure in lb/in.2
α is the pump efficiency; 60% is used for centrifugal pumps

END-OF-CHAPTER SOLVED EXAMPLES

Example 5.1

Assume frictionless flow in a long, horizontal, conical pipe. The diameter is 2.0 ft
at one end and 4.0 ft at the other. The pressure head at the smaller end is 16 ft of
water. If water flows through this cone at a rate of 125.6 ft3/s, find the pressure
head at the larger end.
Fluid Flow and Transport of Fluids 87

Solution
By applying Bernoulli’s equation between the two ends:

p1 g c u2 p g u2
+ Z1 + 1 = 2 c + Z 2 + 2
r g 2g r g 2g

Z1 = Z 2 = 0.0 (horizontal pipe)

V o 125.6 ft 3 /s
V1 = = = 40 ft /s
A1 p(1)2 ft 2

V o 125.6 ft 3 /s
V2 = = = 10 ft /s
A2 p(2)2 ft 2

Substitute in Bernoulli’s equation:

(40)2 p g (10)2
16 + 0.0 + = 2 c + 0 .0 +
2´ 32.17 r g 2´ 32.17

p2 g c
\ Outlet pressure head = = 39.9 ft
r g

Example 5.2

Water is pumped from a large reservoir to a point 65 ft higher than the reser-
voir. How many feet of head must be added by the pump if 8000 lbm/h flows
through a 6 in. pipe and the frictional head loss is 2 ft? The density of the fluid is
62.4 lbm/ft3 and the pump efficiency is 60%. Assume the kinetic energy correction
factor equals 1.
Solution

V2 V2
åF
p1 g p g
+ Z1 + 1 + hW = 2 + Z 2 + 2 +
r g c 2a1g c r g c 2a2g c

Multiply this equation by the factor gc/g to be in terms of head:

p1 g c V2 p g V2
+ Z1 + 1 + hHp = 2 c + Z 2 + 2 +Hf
r g 2a1g r g 2a2g

where
Hp is the pump head
Hf is the frictional head loss
88 Chemical Engineering Primer with Computer Applications

(V22 - V12 ) (p2 - p1) g c

hHp = (Z 2 - Z1) + + +Hf
2g r g

To use the modified form of Bernoulli’s equation, reference points are chosen
at the surface of the reservoir (point 1) and at the outlet of the pipe (point 2).
The pressure at the surface of the reservoir is the same as the pressure at the
exit of the pipe, that is, atmospheric pressure. The velocity at point 1 will be
essentially zero.
Manual solution is presented first, followed by solving the problem by Excel.

Vo m o /r 8000 /(62.4 ´ 3600)

V2 = = = = 0.178 ft /s
A2 p(r)2 ft 2 p(0.25)2 ft 2

((0.178)2 - 0.0)
0.6 ´ Hp = 65 + + 0 .0 + 2
2 ´ 32.17

(V22 - V12 ) (p2 - p1) g c

hHp = (Z 2 - Z1) + + + Hf
2g r g

Hp = 111.66 ft
Fluid Flow and Transport of Fluids 89

Example 5.3

Calculate the diameter of a pipeline handling 10,000 bbl of oil per hour, assuming
that the velocity of flow is about 5 ft/s.
Solution

Q = u(p / 4)d2

[10, 000 bbl/(4.2 ft 3 /bbl)]/3,600 s/h = 5 ft/s [(3.1416/4)d2 ] ft 2

Solving for d = 1.724 ft

Example 5.4

Find the HP for a pump that is handling 500 gpm of oil against a 1000 ft pipeline
with 19 ft equivalent to pipe fittings and valves. Assume friction losses account to
20% of the total head and the specific gravity of the oil is 0.8.
Solution
Total equivalent H = 1000 + 19 + 0.2(1019) = 1223 ft
HP = [(1223)(500)(0.8)]/3960
= 123.5
Brake HB = 123.5/ 0.6
= 206

Example 5.5

1. Manual solution
The pressures at two sections of a horizontal pipe, Sections 1 and 2, are
0.3 and 0.6 kgf/cm2, and the diameters are 7.5 and 15 cm, respectively.
Determine the direction of flow if water flows at a rate of 8.5 kg/s. State
your assumptions.
Data:

Section 1 Section 2

P1 = 0.3 kgf/cm2 P2 = 0.6 kgf/cm 2

D1 = 7.5 cm D2 = 15 cm

Mass flow rate = 8.5 kg/s

Equations
Equation of continuity:

  ρ1A1v1 = ρ2A 2v2

90 Chemical Engineering Primer with Computer Applications

Bernoulli’s equation
For the flow direction from 1 to 2,

p1 v12 p v2
+ + z1 = 2 + 2 + z2 + h + w - q
r1g 2g r2g 2g

Mass flow rate = volumetric flow rate x density

Solution
Volumetric flow rate = 8.5/1000 = 8.5 × 10 −3 m3/s

Section 1 Section 2
-3 -3
V1 = 8.5 ´ 10 /(pD / 4) = 1.924 m/s
2
1 V1 = 8.5 ´ 10 /(pD22 / 4) = 0.481 m/s
P1 = 0.3 kgf/cm2 = 2.9436 × 104 N/m2 P2 = 0.6 kgf/cm2 = 5.8872 × 104 N/m2

Assuming the flow direction is from Section 1 to Section 2:

29.436 ´ 10 4 /1000 + 1.9242 /2 = 5.8872 ´ 10 4 /1000 + 0.4812 /2 + h + w - q

29.436 + 1851
. = 58.872 + 0.116 + h + w - q

In our problem the work done by fluid (w) and pump work on fluid (q)
are zero.
So to balance this equation, the quantity h has to have negative val-
ues. This is not possible. This equation will be a correct one if the flow
is from 2 to 1.

That is, 58.872 + 0.116 = 29.436 + 1851

. +h

Therefore, the flow direction is from the end at which pressure is 0.6 kgf/cm2
and diameter is 15 mm to the end at which pressure is 0.3 kgf/cm2 and
diameter is 7.5 mm.

2. Excel solution

Given
P1 = 0.3 kgf/cm2 P1 = 29,420.4178 N/m2
P2 = 0.6 kgf/cm2 P2 = 58,840.8355 N/m2
D1= 7.5 cm V1 = 0.0001925 m/s
D2 = 15 cm V2 = 0.0000481 m/s
Water flow rate = 8.5 kg/s Volumetric flow rate = 0.0085 m3/s

p1 v12 p v2
+ + z1 = 2 + 2 + z2 + h + W - q
r1g 2g r2g 2g
Fluid Flow and Transport of Fluids 91

h + w − q = −29.42041775253
w=0
q=0
h = −29.420
The previous equation will be a correct one if the flow is from 2 to 1.
Therefore the flow direction is from the end at which pressure
is 0.6  kgf/cm2 and diameter is 15  mm to the end at which pressure is
0.3 kgf/cm2 and diameter is 7.5 mm.

Example 5.6

A simple force balance on a spherical particle reaching terminal velocity in a fluid

is given by

Vt = ((4g(rp - r)Dp ) / (3CDp)) ^ 5

where
Vt is the terminal velocity in m/s
g is the acceleration due to gravity
pp is the particle density
Dp is the diameter of the spherical particle in m
CD is the dimensionless drag coefficient

The drag coefficient on a spherical particle at terminal velocity varies with Re

number as the follows:
CD = 24/Re For Re < 0.1
CD = 24 ∗ (1 + 014 ∗ Re^7)/Re For 0.1 ≤ Re ≤ 1,000
CD = 0.44 For 1,000 < Re ≤ 350,000
CD = 0.19−8 ∗ 10^4/Re For 350,000 < Re
where
Re = (DpVtp)/µ
g = 9.80665 m/s2
ρ = 994.6 kg/m3
pp = 1800 kg/m3
µ = 8.931 × 10 −4 kg/m ⋅ s
Dp = 0.000208

Calculate the terminal velocity of spherical particle.

Solution
This problem cannot be solved without using a trial and error procedure. Therefore,
you must assume a velocity to calculate the CD that is important to calculate a new
velocity. Write the following code:

g = 9.80665; p = 994.6; pp = 1800; mu = 8.931e‐4; Dp =

0.000208;
% Assume vt of any initial terminal velocity for first
trail vt = 1;
92 Chemical Engineering Primer with Computer Applications

Velocity(1) = vt;
for m = 1:1:20
Re = (Dp*vt*p)/mu;
if Re < 0.1
CD = 24/Re;
elseif Re ≥ 0.1 & Re ≤ 1000
CD = 24*(1 + 014*Re^7)/Re;
elseif Re>1000 & Re ≤ 350,000
CD = 0.44;
elseif Re>350,000
CD = 0.19−8*10^4/Re;
end
vt = ((4*g*(pp‐p)*Dp)/(3*CD*p))^5;
Velocity(m + 1) = vt;
if abs (Velocity(m + 1)−Velocity(m))<.0001
break end
end
Velocity’

This code gives the following result

ans =
1.0000
0.0538
0.0251
0.0190
0.0170
0.0163

Example 5.7

Calculate the minimum area and diameter of a thickener with a circular basin to
treat

Solid Concentration (kg/m3) Settling Velocity (μm/s)

100 148
200 91
300 55.33
400 33.25
500 21.4
600 14.5
700 10.29
800 7.33
900 5.56
1000 4.2
1100 3.27
Fluid Flow and Transport of Fluids 93

0.1 m3/s of a slurry of a solid concentration of 150 kg/m3. The results of batch set-
tling tests are as follows:
160
140
120
100
80
u

60
40
20
0
0 150 300 450 600 750 900 1050 1200 1350 1500
G

0.02
0.018
0.016
0.014
0.012
0.01
0.008
0.006
0.004
0.002
0
0 150 300 450 600 750 900 1050 1200 1350 1500

A value of 1290 kg/m3 for underflow concentration was selected from a retention

time test. Estimate the area and the diameter of the thickener and the underflow
volumetric flow rate assuming total separation of all solids and clear overflow is
obtained.
Solution
The settling rate of the solids, G kg/m2s , is calculated as G = usc, where us is the
settling velocity (m/s) and c the concentration of solids (kg/m3), and the data are
plotted as shown in the diagram. From the point u = 0 and c = 1290 kg/m3, a line
is drawn that is tangential to the curve. This intercepts the axis at G.

G = 0.0154 kg/m2s

The area of the thickener is then

A = (0.1´ 150)0.0154 = 974 m2

94 Chemical Engineering Primer with Computer Applications

and the diameter is

d = [(4 ´ 974) /p]^ 05 = 352 m

The volumetric flow rate of underflow, obtained from a mass balance, is

= [(0.1´ 150)/1290] = 0.0116 m3 /s

REFERENCES
FAO Corporation Document Repository, Water lifting devices, pump classifications. Fao.org.,
http://www.fao.org/docrep/010/ah810e/AH810E05.htm\l5.3.1, retrieved on May 25, 2011.
Hydraulic Institute, http://www.pumps.org/, retrieved on May 25, 2011.
 6 Heat Transmission

Fourier’s law: Rate of transfer in a

process = driving force/ resistance
Q = kAavg∆T/∆x
Conduction
Three mechanisms by which heat (energy) is transferred: Convection
Radiation
Q = hA∆T
Classification
of heat Q = AT4
exchangers

They are classified by:

Parallel Counter
Flow arrangement: Three types Cross flow
flow current flow
Construction
Degree of compactness
TA > TB
q (T2 – t1)–(T1 – t2)
Overall Ht.Tr. ∆Tlm =
coefficient: T2 – t1
ln
Fluid A Fluid B T1 – t2
Q = UA∆Tlm

Convection: A wall
Conduction: Through wall
Convection: wall B
Heat Trans Mechanism in HT.
Exchangers

6.1 INTRODUCTION
Heat transfer, as a topic, is concerned with two main items:

1. Temperature
2. Flow of heat

Whenever a temperature difference exists in a medium or between media, heat

transfer must occur. Temperature represents the amount of thermal energy available,
whereas heat flow represents the movement of thermal energy from place to place.

95
96 Chemical Engineering Primer with Computer Applications

Heat transfer always occurs from a region of high temperature to another region
of lower temperature. Heat transfer changes the internal energy of both systems
involved according to the first law of thermodynamics. Heat transfer is a process
function (or path function), as opposed to functions of state; therefore, the amount
of heat transferred in a thermodynamic process that changes the state of a system
depends on how that process occurs and not only on the net difference between the
initial and final states of the process.

6.2 MODES OF HEAT TRANSFER

The fundamental modes of heat transfer are as given.

Conduction Convection Radiation

In many practical problems, these three mechanisms combine to generate the total
energy flow.

1. Conduction: The transfer of energy between objects that are in physical

contact. Thermal conductivity is the property of a material to conduct
heat. It is evaluated primarily in terms of Fourier’s law for heat conduc-
tion. Regions with greater molecular kinetic energy will pass their thermal
energy to regions with less molecular energy through direct molecular colli-
sions, a process known as conduction. In metals, a significant portion of the
transported thermal energy is also carried by conduction-band electrons.
Conduction happens in solids and fluids (direct contact between neighbor-
ing atoms or molecules through intervening matter without bulk motion of
the matter).
2. Convection: The transfer of energy between an object and its environment,
due to fluid motion. The average temperature is a reference for evaluating
properties related to convective heat transfer.
Convective heat transfer, or convection, is the transfer of heat from one
place to another by the movement of fluids, a process that is essentially
the transfer of heat via mass transfer. Bulk motion of fluid enhances heat
transfer in many physical situations, such as between a solid surface and
the fluid. Convection is usually the dominant form of heat transfer in liq-
uids and gases. Although sometimes discussed as a third method of heat
transfer, convection is usually used to describe the combined effects of heat
conduction within the fluid (diffusion) and heat transference by bulk fluid
flow streaming.
Heat Transmission 97

3. Radiation: The transfer of energy from the movement of charged particles

within atoms is converted to electromagnetic radiation. Thermal radiation
occurs through a vacuum or any transparent medium (solid or fluid). It is
the transfer of energy by means of photons in electromagnetic waves gov-
erned by the same laws. Thermal radiation is energy emitted by matter as
electromagnetic waves, due to the pool of thermal energy in all matter with
a temperature above absolute zero. Thermal radiation propagates without
the presence of matter through the vacuum of space.

6.3 HEAT TRANSFER BY CONDUCTION

6.3.1 Fourier’s law
In all transport processes, such as momentum, heat, and mass transfer, the basic rate
of transfer is determined by the following formula:

Rate of transfer in a process = Driving force/resistance

Fourier’s law is the fundamental differential equation for heat transfer by conduction:
dq dT
= Q = - kA (6.1)
dq dx

where
dq/dθ is the rate of flow of heat
Q is the quantity per unit time
A is the area at right angles to the direction of heat flow
−dT/dx is the rate change of temperature with a distance (temperature gradient)
k is the thermal conductivity, which is a function of the material through which
heat flows

The equation for the case of one-dimensional steady-state heat conduction, Figure
6.1, is obtained as follows:

1. Rearranging Equation 6.1:

Qdx
= - kdT (6.2)
A
2. Integrating Equation 6.2 between the limits x1 – x2 and T1 – T2:

Q = kA avg DT / Dx (6.3)

There are several ways to correlate the geometry, physical properties, and tempera-
ture difference of an object with the rate of heat transfer through the object. In heat
transfer by conduction, the most common means of correlation is through Fourier’s
law of conduction. The law, stated by the equation, is applicable most often in objects
98 Chemical Engineering Primer with Computer Applications

T1 T2 < T1

dT
dx

FIGURE 6.1 1D conduction.

of rectangular or cylindrical form (e.g., pipes and cylinders). Equation 6.3 is used for
the case of those of rectangular form, while Equation 6.4 is designated for those of
cylindrical form:

æ DT ö
Q = - kA ç ÷ (6.4)
è Dr ø

where
Q is the rate of heat transfer (Btu/h)
Q/A is the heat flux (Btu/h · ft2)
A is the cross-sectional area of heat transfer (ft2)
x is the thickness of slab (ft)
r is the thickness of cylindrical wall (ft)
T is the temperature difference (°F)
k is the thermal conductivity of slab (Btu/h · ft · °F)

6.3.2 tHermal conductivity

The heat transfer characteristics of a solid material are measured by a property
called the thermal conductivity (k) measured in Btu/h · ft · °F. It is a measure of a
substance’s ability to transfer heat through a solid by conduction. The thermal con-
ductivity of most liquids and solids varies with temperature. For vapors, it depends
upon pressure. Thermal conductivity varies with temperature but not always in the
same direction.
Heat Transmission 99

6.3.3 conduction tHrougH a Hollow cylinder

In many applications in the process industry, the need arises to calculate the heat
transfer through a thick-walled cylinder, as in pipes. Consider a hollow cylinder with
an inside radius r1, where the temperature is T1, and an outside radius r2, where
the temperature is T2, having a length L measured in meters. Heat is flowing radi-
ally from the inside surface to the outside. Equation 6.4, as given earlier, is readily
applied, with distance dr instead of dx.
It can be shown that the final equation to be used is

T1 - T2
Q = kA lm
r2 - r2

where Alm refers to the log mean area = (A2 − A1)/ln (A1/A2).

6.3.4 conduction tHrougH solids in series

In the case of a multilayer wall of more than one material present, for example, with
three layers, having resistances R A, RB, and RC and a driving force of T1 − T4, the
final equation to be used is represented as

Q = [(DT) : T1 - T4 ]/sum of the individual resistances of eac h wall

Q = [T1 - T4 ]/{R A + R B + R C}

6.3.5 solved examPles

Example 6.1

The heat transfer rate through a section of insulating material (as shown in Figure
6.2) that measures 1 ft 2 in cross-sectional area is equal to 1000 Btu/h. The thick-
ness is 1 in. and the thermal conductivity is 0.12 Btu/h · ft · °F.

(a) Compute the temperature difference across the material.

(b) Show the temperature profile along the distance by using MATLAB®,
assuming the initial temperature To = 400°F.

Solution

 = kA æ DT ö
(a) Q ç X÷
èD ø
Solving for ΔT,

 æ DX ö
DT = Q ç kA ÷
è ø
1000 (Btu/h)(1/12 ft )
DT =
0.12 Btu/h × ft × °F
100 Chemical Engineering Primer with Computer Applications

Insulating
material

.
Q = 1000 Btu/h
A = 1 ft2

k = 0.12 Btu/h ft °F

∆x
1 in.

FIGURE 6.2 Conduction through a slab.

(b) Calculations by MATLAB (see Figure 6.3)

 x =[0 : 0.01 : 1/12]

 q = 1000

 k = 0.12

 a=1

 temperature = 800 [q.*x][

/ k*a]

temperature = 1.0e + 002*

800
60
700
50
Temperature (°F)

600
500 40

400 30
300 20
200 10
100
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Distance (deltaX)

FIGURE 6.3 Distance versus temperature at steady state.

Heat Transmission 101

Columns 1 through 6
8.000000000000000 7.166666666666666 6.333333333333332
5.500000000000000 4.666666666666666 3.833333333333333
Columns 7 through 9
3.000000000000000 2.166666666666666 1.333333333333333
≫ plot(x,temperature)
>

Example 6.2

A concrete floor with a conductivity of 0.8 Btu/h · ft · °F measures 30 ft by 40 ft

with a thickness of 4 in. The floor has a surface temperature of 70°F and the
temperature beneath it is 60°F. What are the heat flux and the heat transfer rate
through the floor?
Solution

A direct application of Q = q/A = -k{DT/Dx}

= 0.8(10 / 0.333)

= 24 Btu/h × ft 2

6.4 HEAT TRANSFER BY CONVECTION

6.4.1 introduction
Convection involves the transfer of heat by the motion and mixing of macroscopic
portions of a fluid (i.e., the flow of a fluid past a solid boundary). The term natural
convection is used if this motion and mixing is caused by density variations resulting
from temperature differences within the fluid. The term forced convection is used
if this motion and mixing is caused by an outside force, such as a pump or fan (as
shown in Figure 6.4). The transfer of heat from a hot-water radiator to a room is an
example of heat transfer by natural convection. The transfer of heat from the surface

Ceiling

Free convection cell

Radiator

Floor
Solid surface
Natural convection Forced convection

FIGURE 6.4 Schematic of natural convection versus forced convection.

102 Chemical Engineering Primer with Computer Applications

of a heat exchanger to the bulk of a fluid being pumped through the heat exchanger
is an example of forced convection.
Heat transfer by convection is more difficult to analyze than heat transfer by con-
duction because no single property of the heat transfer medium, such as thermal
conductivity, can be defined to describe the mechanism. Heat transfer by convection
varies from situation to situation (upon the fluid flow conditions), and it is frequently
coupled with the mode of fluid flow.
In practice, the analysis of heat transfer by convection is treated empirically (by
direct observation). Convection heat transfer is treated empirically because of the
factors that affect the stagnant film thickness such as fluid velocity, fluid viscosity,
heat flux, surface roughness, and the type of flow (single phase/double phase).

6.4.2 metHodology oF calculation

Convection involves the transfer of heat between a surface at a given temperature
(Ts) and fluid at a bulk temperature (Tb). The exact definition of the bulk temperature
(Tb) varies depending on the details of the situation. For flow adjacent to a hot or
cold surface, Tb is the temperature of the fluid far from the surface. For boiling or
condensation, Tb is the saturation temperature of the fluid. For flow in a pipe, Tb is
the average temperature measured at a particular cross section of the pipe.
The basic relationship for heat transfer by convection has the same form as that
for heat transfer by conduction:

Q = hADT

where
Q is the rate of heat transfer (Btu/h)
h is the convective heat transfer coefficient (Btu/ft2 · °F)
A is the surface area for heat transfer (ft2)
ΔT is the temperature difference (°F)

6.4.3 convective Heat transFer coeFFicient

The convective heat transfer coefficient (h), defines, in part, the heat transfer due to
convection. The convective heat transfer coefficient is sometimes referred to as a
film coefficient and represents the thermal resistance of a relatively stagnant layer of
fluid between a heat transfer surface and the fluid medium. Common units used to
measure the convective heat transfer coefficient are Btu/h · ft2 · °F.
The convective heat transfer coefficient (h) is dependent upon the physical prop-
erties of the fluid and the physical situation. Typically, the convective heat transfer
coefficient for laminar flow is relatively low compared to the convective heat transfer
coefficient for turbulent flow. This is due to turbulent flow having a thinner stagnant
fluid film layer on the heat transfer surface. Values of h have been measured and
tabulated for the commonly encountered fluids and flow situations occurring during
heat transfer by convection.
Heat Transmission 103

Example 6.3

An uninsulated steam line, 22 ft long, crosses a room. The outer diameter of the
steam line is 18 in. and the outer surface temperature is 280°F. The convective
heat transfer coefficient for the air is 18 Btu/h · ft 2 · °F. Calculate the heat transfer
rate from the pipe into the room if the room temperature is 72°F.
Solution

Q = hADT
= h(2prL)DT
( )
= 18 Btu/h × ft 2 × °F ( 2(3.14)(0.75 ft)(22 ft) ) (280 °F - 72°F)
5
= 3.88 ´ 10 Btu / h

6.5 OVERALL HEAT TRANSFER COEFFICIENT

6.5.1 Background
Many of the heat transfer processes encountered in nuclear facilities involve a com-
bination of both conduction and convection. For example, heat transfer in a steam
generator involves convection from the bulk of the reactor coolant to the steam gen-
erator inner tube surface, conduction through the tube wall, and convection from the
outer tube surface to the secondary side fluid.
In cases of combined heat transfer for a heat exchanger, there are two values for h.
There is the convective heat transfer coefficient hi for the fluid film inside the tubes
and a convective heat transfer coefficient h0 for the fluid film outside the tubes. The
thermal conductivity, k, and thickness, Δx, of the tube wall must also be accounted
for. An additional term Uo, called the overall heat transfer coefficient, must be used
instead. It is common practice to relate the total rate of heat transfer, Q to the cross-
sectional area for heat transfer Ao and the overall heat transfer coefficient Uo. The
relationship of the overall heat transfer coefficient to the individual conduction and
convection terms is shown in Figure 6.5.

6.5.2 discussion
Recalling the basic equation for the quantity of heat transfer per unit time:

Q = U o ADT

An example of Uo concept applied to cylindrical geometry is illustrated in Figure 6.6,

which shows a typical combined heat transfer situation.
Using the figure representing flow in a pipe, it is found that

• Heat transfer by convection occurs between temperatures T1 and T2

• Heat transfer by conduction occurs between temperatures T2 and T3
• Heat transfer occurs by convection between temperatures T3 and T4
104 Chemical Engineering Primer with Computer Applications

Fluid A

Fluid B
TA
.
. Q
Q T1 T2 TA T1 T2 TB
h1 h2
TB 1 ∆x 1
k
h1 A kA h2 A
∆x
. TA – TB
Q=
1/h1A + ∆x/kA + 1/h2A
.
Q = UoA∆Toverall

1
Uo =
1/h1 + ∆x/k + 1/h2

FIGURE 6.5 Relationships between U and individual conduction and convection terms.

T3 T4
∆r

T2

T1
A1

Tube
A2

FIGURE 6.6 Example for the illustration of the concept of Uo cylindrical geometry.

Thus, there are three processes involved. Each has an associated heat transfer coef-
ficient, cross-sectional area for heat transfer, and temperature difference. The basic
relationships for these three processes can be expressed as follows:

 = h1A1 (T1 - T2 )
Q

k
Q = A lm (T2 - T3 )
Dr

Q = h 2 A 2 (T3 - T4 )

ΔTo can be expressed as the sum of the three individual processes:

DTo = (T1 - T2 ) + (T2 - T3 ) + (T3 - T4 )

Heat Transmission 105

If the basis relationship for each process is solved for its associated temperature dif-
ference and substituted into the expression for ΔT, the following relationship results:

æ 1 Dr 1 ö
DTo = Q ç + + ÷
h A
è 1 1 kA lm h 2A2 ø

This relationship can be modified by selecting a reference cross-sectional area Ao:

Q æ A o DrA o Ao ö
DTo = + +
A o çè h1A1 kA lm h 2 A 2 ÷ø

Solving for Q results in an equation in the form Q = U o A o DTo

1
Q = A o DTo
æ Ao DrA o Ao ö
çhA + + ÷
è 1 1 kA lm h 2 A 2 ø

or

Q = UADT

where

1
U=
æ Ao DrA o Ao ö
ç h A + kA + h A ÷
è 1 1 lm 2 2 ø

Example 6.4

Calculate the heat rate per foot of a tube from a condenser under the follow-
ing conditions. T = 232°F and the outer diameter of the copper condenser tube
is 0.75 in. with a wall thickness of 0.1 in. Assume the inner convective heat
transfer coefficient is 2000  Btu/h · ft 2 · °F and the thermal conductivity of cop-
per is 200  Btu/h · ft · °F. Also, the outer convective heat transfer coefficient is
1500 Btu/h · ft · °F.
Solution

1
Uo =
(1/h1) + (Dr/k) + (1/h2 )
1
=
(1/ 2000) + (0.1 in./200)(1 ft/12 in.) + (1/1500)

= 827.6 Btu/h × ft 2 × °F
106 Chemical Engineering Primer with Computer Applications

 = U A DT
Q o o lm


Q U A DT
= o o lm
L L
= Uo 2prDTlm
æ 1 ft ö
( )
= 827.6 Btu/h × ft 2 × °F (2p)(0.375 in.) ç ÷ (232°F)
è 12 in. ø
= 37, 700 Btu/h × ft

6.6 HEAT TRANSFER BY RADIATION

6.6.1 introduction
While both conductive and convective transfers involve the flow of energy through
a solid or fluid substance, no medium is required to achieve radiative heat trans-
fer. As a matter of fact, electromagnetic radiation travels more efficiently through a
vacuum. The thermal radiation band is shown within the electromagnetic spectrum
in Figure 6.7.
Radiant heat transfer involves the transfer of heat by electromagnetic radia-
tion that arises due to the temperature of a body. Most energy of this type is in the
infrared region of the electromagnetic spectrum although some of it is in the visible
region. The term thermal radiation is frequently used to distinguish this form of elec-
tromagnetic radiation from other forms, such as radio waves, x-rays, or gamma rays.
The transfer of heat from a fireplace across a room in the line of sight is an example
of radiant heat transfer.

Thermal
radiation X-ray
log λ (m)

3 2 1 0 –1 –2 –3 –4 –5 –6 –7 –8 –9 –10 –11 –12

Ultra
Infrared
violet
Radio waves γ rays

Visible light

FIGURE 6.7 Band of thermal radiation within the electromagnetic spectrum.

Heat Transmission 107

6.6.2 BlackBody radiation

A body that emits the maximum amount of heat for its absolute temperature is called
a blackbody. Radiant heat transfer rate from a blackbody to its surroundings can be
expressed by the following equation:

Q = FAT 4 (6.5)

where
Q is the heat transfer rate (Btu/hr)
Φ is the Stefan–Boltzmann constant (0.174 Btu/hr · ft2 · °R4)
A is the surface area (ft2)
T is the temperature (°R)

6.7 HEAT EXCHANGERS

6.7.1 tyPes oF Heat excHangers
Heat exchangers are defined as thermal devices that transfer or exchange heat from
one fluid to another. They are classified either by

• Flow arrangement
• Construction
• Degree of compactness

We will elaborate on the classification by flow arrangement. Three types are known:

1. Parallel flow: Both fluids run side by side in the same direction.
2. Countercurrent flow: Similar to parallel flow, except the streams go in the
opposite side to each other.
3. Cross flow: Here, we have the two-flow stream normal to one another.

In recuperative heat exchangers, mixing and contamination is prevented by solid

walls. The dominant mechanism of heat transfer is illustrated in Figure 6.8.

TA > TB
q
Convection: A wall
Conduction: Through wall
Convection: wall B Fluid A Fluid B

FIGURE 6.8 Heat transfer mechanism in heat exchangers.

108 Chemical Engineering Primer with Computer Applications

Inlet Inlet
Exit
Th, i Th, i

Hot Hot Exit

Th, o Exit Tc, o Th, o

T
T

Tc, o
Cold Inlet
Cold Tc, i
Tc, i
(a) Distance along heat exchanger, x (b) Distance, x

FIGURE 6.9 Temperature distribution in both flow arrangements. (a) Parallel flow and
(b) counterflow.

Secondary
fluid out
Steam in

Shell
Channel
(end box or header) U-tube bundle
Pass partitions

Condensate
Secondary
out
U-tube fluid in

FIGURE 6.10 U-type heat exchanger.

Temperature distribution for parallel flow and counterflow is illustrated in

Figure 6.9.
The two well-known types, U-type and the shell and tube heat exchangers, are
diagrammatically shown in Figures 6.10 and 6.11, respectively.

6.7.2 log mean temPerature diFFerence

In heat exchanger applications, the inlet and outlet temperatures are commonly spec-
ified based on the fluid in the tubes. The temperature change that takes place across
the heat exchanger from the entrance to the exit is not linear. A precise temperature
change between two fluids across the heat exchanger is best represented by the log
mean temperature difference (LMTD) or ΔTlm, given by following equation:

(T2 - t1 ) - (T1 - t 2 )
DTlm = (6.6)
ln ( (T2 - t1 ) / (T1 - t 2 ) )
Heat Transmission 109

Tube Shell
outlet inlet Baffles

Shell Tube
outlet inlet
Shell and tube

FIGURE 6.11 Shell and tube heat exchanger.

where
T1 is the temperature of hot fluid stream at the entrance
T2 is the temperature of hot fluid stream at the exit
t1 is the temperature of cold fluid stream at the entrance
t2 is the temperature of cold fluid stream at the exit

6.7.3 design oF Heat excHangers

The simplest answer to give for what is meant by the design of a heat exchanger is to
find the value of “A” using the following relationship:

Q = UADT

Given: Q, U, ΔT
Find: A
Now, it is not that simple to find the area of a heat exchanger.
The thermal design of a shell and tube HE is briefly described by the following
procedure:

1. Consideration of process fluids in both shell and tube sides

2. Selection of the required temperature specifications
3. Limiting the shell and tube side pressure drop
4. Setting shell and tube side velocity limits
5. Finding heat transfer area including fouling factor

In addition, to carry out your design, it would require the following input:

1. Mass flow rate

2. Heat duty
110 Chemical Engineering Primer with Computer Applications

3. Shell-side inlet temperature

4. Shell-side outside temperature
5. Tube-side inlet temperature
6. Tube-side outlet temperature
7. Heat transfer coefficient
8. Tube outside diameter
9. Length of tube

Example 6.5

A liquid-to-liquid countercurrent flow heat exchanger is used as part of an aux-

iliary system at a nuclear facility. The heat exchanger is used to heat a cold fluid
from 120°F to 310°F.
Assuming that the hot fluid enters at 500°F and leaves at 400°F, calculate the
LMTD for the exchanger.
Solution

DT2 = 400°F - 120°F = 280°F

DT1 = 500°F - 310°F = 190°F

DT2 - DT1
DTlm =
ln ( DT2 /DT1 )

(280°F - 190°F)
=
ln ( 280°F/190°F )

= 232°F

END-OF-CHAPTER SOLVED EXAMPLES

Example 6.6

Consider a rectangular plate with some heat sources on each edge. Assuming
these heat sources remain constant, the plate will eventually reach an equilib-
rium temperature. We will assume a constant heat source, while the ambient
air is staying at a constant temperature. This would make one side of the cube
to gain a very high temperature and the other five sides a relatively low tem-
perature (room temperature). We are, of course, ignoring any fans or buildup of
heat within the enclosure. The 2D analog to this problem would be some cross
sections cut out from this cube. Consider discretizing our rectangular plate with
a rectangular grid (Figure 6.12). To determine the equilibrium, we may assume
that if the plate is at equilibrium and xi is a grid point not on the boundary,
then the temperature at xi is given by the average of the temperatures of the
four closest grid points to xi. This creates a linear system for xi, which we can
then solve.
This problem corresponds to solving a partial differential equation using finite
differences in two dimensions using MATLAB.
Heat Transmission 111

20°C

x3 x4
20°C 20°C
x1 x2

50°C

FIGURE 6.12 Rectangular plate with different heat sources on each edge.

Hint: The temperature at any point will be given by the average of the four tem-
peratures around it.
Solution
Given:
The temperature at each point (say x1, x2, x3, and x4) is the average of the adjacent
four points:

50+20+x2+x3
x1 =
4

In the same way,

x4+x1+50+20 x1+x4+20+20 x3+x2+20+20

x2 = , x3 = , x4 =
4 4 4

Now, make it in linear form:

4x1  x2  x3  0x4 = 70
 x1 + 4x2 + 0x3  x4 = 70
 x1 + 0x2 + 4x3  x4 = 40
0x1  x2  x3 + 4x4 = 40

This can be solved by using MATLAB:

A = [4 1 10 ;  14 0 1 ; 10 4 1 ; 0 1 14]

B =[70; 70; 40; 40]

X = A\B

X = 31.2500
= 31.2500
= 23.7500
= 23.7500
112 Chemical Engineering Primer with Computer Applications

Example 6.7

Water at the rate of 30,000 Ibm/h is heated from 100°F to 130°F in a shell and
tube heat exchanger. On the shell side, one pass is used with water entering as the
working fluid that is heated at a flow rate of 15,000 Ibm/h at 200°F.
Given: Uo = 250 Btu/h · ft 2 · °F and the average water velocity in the ¾ in. 1D tubes
is 1.2 ft/s.
Find: The total area, A; the number of tubes, n; and the length of the tube, L,
assuming countercurrent flow and one tube pass is used
Solution (Manual)
The exit temperature of the hot water is unknown and to be calculated by

Q = mccpDt c = mhcpDt h

Therefore, Δth = 60 and texit = 140°F.

Next, we calculate ΔTlm. We found its value to be equal to 53.6°F.
Then, we can get the total area, A:

Q = mccpDt c = 30, 000 ´ 1´ 30 = 9 ´ 105 Btu/h

= UADTlm

9 ´ 105
A= = 67.3 ft 2
250 ´ 53.6

The cross sectional area of flow, S, in ft 2, is calculated, given velocity in ft/h and
density in Ibm/ft3 and mc = 30.000 lbm/h:

Therefore,

30, 000
S= = 0.111ft 2
62.4 ´ 12
. ´ 3600

where S is equal to the number of tubes (n) multiplied by the flow area per tube,
that is,

S = n × (π/4)(d2)

Therefore, n = 36.
Excel Solution

Water density = 62.4 d = 0.75

U = 250 Velocity = 1.2
mc = 30,000 mh = 15,000
Cp = 1 Cp = 1
tcold−out = 130 tcold−in = 100
Δt − cold = 30 thot−in = 200
Heat Transmission 113

Calculations

Q = 900,000 thot−out = 140

S = 0.1113 Δt − hot = 60
n = 36.293 ΔtLM = 53.608
A = 67.154

Estimate a relation between the variation of the number of tubes and the fluid velocity.

V n
0.2 217
0.5 87
0.8 54
1.1 40
1.2 36
1.5 29
1.8 24

Variation of number of tubes with changing fluid velocity

250
200 n = 198.82v–1.102
Number of tubes

150 R2 = 0.9903

100
50
0
0.2 0.5 0.8 1.1 1.2 1.5 1.8
Fluid velocity ft/s

Example 6.8

An electrically heated element of surface area 12 cm2 is completely immersed in a

fluidized bed. The resistance of the element is measured as a function of the volt-
age applied to it, thus arriving at the following data:

Potential (V) 1 2 3 4 5 6
Resistance (Ω) 15.47 15.63 15.91 16.32 16.83 17.48

The relation between resistance Rw and temperature Tw is

Rw
= 0 .004 Tw - 0.092,
R0
114 Chemical Engineering Primer with Computer Applications

where
R0 is the resistance of the wire (equal to 14 Ω) at 273 K
Tw is in K

Estimate the bed temperature and the value of the heat transfer coefficient between
the surface and the bed.
Solution
The heat generation rate by electrical heating is (V2)/R.
The rate of heat dissipation is hA(Tw − TB),
where Tw and TB are the wire and bed temperatures, respectively.
At equilibrium,

(V 2 ) /Rw = hA(Tw - TB)

But

Rw
= 0.004Tw - 0.092
R0

so that

æ Rw ö
Tw = 250 ç ÷ + 23
è R0 ø

Thus,

æ Rw ö
(V 2 ) = ç 250hARw - (hARw(TB - 23)),
è R0 ÷ø

where Rw is a mean value of Rw noting that the mean cannot be used inside the
bracket in the equation for Tw.
Thus, a plot of (V2) against Rw should yield a line of slope = 250hARw/R0 as given
in the next diagram, from which the value of the slope is found to be 17.4.
Hence,

17.4 ´ 14
h= = 49.2 W/m2K
250 ´ 12 ´ 10 -4 ´ 16.5

The bed temperature is found by the intercept at (V2) = 0, that is, when

Rw = 15.4 W

Thus,

TB = 250(15.4/14) + 23 = 298 K

Area = 12 cm2

R0 at 273 K = 14 Ω
Heat Transmission 115

Potential (V) Resistance (Rw) (V2)

1 15.47 1
2 15.63 4
3 15.91 9
4 16.32 16
5 16.83 25
6 17.48 36

At equilibrium, (V2)/Rw = hA(Tw − TB)

Rw
= 0 .004Tw - 0.092
R0

so that

Rw
Tw = 250 + 23
R0

Thus,

æ Rw ö
(V 2 ) = ç 250hARw - (hARw(TB - 23))
è R0 ÷ø

40

35

30

25
y = 17.388x – 267.79
20
V2

R2 = 0.9999
15

10

0
15 15.5 16 16.5 17 17.5 18
Resistance, Rw

where Rw is a mean value of Rw noting that the mean cannot be used inside the
bracket in the equation for Tw.
Thus, a plot of (V2) against Rw should yield a line of slope = 250hARw /R0. This
is shown in the figure from which the value of the slope is 17.4

h = 49.21 W/m2K
116 Chemical Engineering Primer with Computer Applications

The bed temperature is found by the intercept at (V2) = 0 that is when Rw = 15.4 Ω

Rw = 15.4 Ω

TB = 298 K

Example 6.9

Write a program to estimate the physical properties for water in the range of tem-
peratures from 273 to 323 K.
The density for water in the range of

r = 1200.92 - 1.0056T + 0.001084T2

The conductivity K = 0.34 + 9.278* 10 −4T

The specific heat CP = 0.015539(T – 308.2)2 + 4180.9

Note: Take 101 points of temperatures

Solution
T = 273:.5:323;
%The density
P = 120,092 − 10,056* T + 0001084* T2;
%The conductivity
K = 034 + 9278* 10 −4* T;
%The specific heat
CP = 0015539* (T − 3082)2 + 4180.9;
A = [T′,P′,K′,CP′]

6A APPENDIX: INTERNAL-FLOW CONVECTION CORRELATIONS

This workbook computes the Nusselt number for forced convection in a circular pipe
as a function of the Reynolds (based on diameter) and Prandtl numbers (and where
appropriate one or two other parameters). It includes subroutines for laminar, transi-
tion, and turbulent flows and for liquid metals. Results for a range of Reynolds and
Prandtl numbers are shown in this plot. This spreadsheet was developed to aid in
verifying our internal-flow module (Ribando, 1998).
Heat Transmission 117

Nusselt vs. Reynolds number

1.E+05

1.E+04
Nusselt number

1.E+03

Pr = 1000
1.E+02 Pr = 100
Pr = 10
Pr = 1
1.E+01 Pr = 0.05
Pr = 0.005
Your value
1.E+00
1.E+02 1.E+03 1.E+04 1.E+05 1.E+06
Reynolds number

REFERENCE
Ribando, R.J. An excel/visual basic for applications (VBA) primer, Computers in
Education Journal, VIII(2): 38–43, April–June 1998 [A version of this article
updated for Excel 2007].
 7 Two-Phase Gas–Liquid
Diffusional Operations
Distillation and Absorption

Liquid–gas contacting systems, in general, are utilized for transferring mass, heat,
and momentum between the phases, subject to constraints of physical and chemical
equilibrium.
Emphasis is placed in this chapter on the diffusional transfer of mass between
phases, known as interphase operations. The transfer of mass from one phase to
another is involved in typical liquid–gas mass transfer operations described as
follows:

• Distillation (fractional distillation) is the most widely used separation

process in the chemical industry. Distillation (also known as fractional
distillation) is the separation of a mixture into its component parts, or
fractions. Separating chemical compounds by their boiling point by heat-
ing them to a temperature at which one or more fractions of the compound
will vaporize is distillation, where the constituents or the component of
the mixture boil at less than 25°C from each other under a pressure of
1 atm.
• Flashing is a single-stage distillation process in which the total vapor
removed is kept in intimate contact with the liquid, allowing for equilib-
rium to be established between the vapor and liquid.
• Rectification is the separation of the constituents of a liquid mixture by suc-
cessive distillation (implying vaporization and condensation). Separation
into effectively pure components may be obtained.
• Absorption is the transfer of a solute component in a gas-phase stream into
a liquid absorbent (solvent).
• Stripping (desorption) is the transfer of gas, dissolved in a liquid, into a gas
stream.

Distillation and absorption, as two main unit operations, are covered in this chapter.

119
120 Chemical Engineering Primer with Computer Applications

One page summary for distillation

Packed column

Based on column Tray column:

internals 1. Bubble cap 2. Valve 3. Sieve

Binary
Atm P
Based on number of Complex
components in feed Multi
Based on
Hi P design pressure
Single stage
Based on nNumber
Vac. of stages:
Multistage

Two streams:
simple Based on Classification,
stream concepts and tech.
Side streams: no.
comple aspects
Interphase operation?
Transfer of mass from one
Change in phase phase to another in distillation
Separation using distillation and absorption operations is an
and absorption requires interphase operation.
Distillation
change in phase.

Design aspects
N = number of trays, D = diameter
In column design:
N = f (degree of
Design of columns based on
separation)
equilibrium-stage concept involves 3
Major steps: D = f (capacity)
1. Collect thermodynamic V/L
equilibrium data
2. Calculate NT (theor.no. of stages) Two physical models are used
in the design analysis of
3. Find efficiency and convert NT to
distillation columns:
NA(actual no. of stages)
Two key factors to be 1. Equilibrium stage model:
considered in column (finite stage contactors)
design are:
Tray efficiency: It 2. Continuous contact model:
1. Operating pressure
describes the extent to (Differential stage contactors)
2. Reflux ratio
which performance of
NA duplicates
performance of NT

7.1 PART I: DISTILLATION

7.1.1 introduction
7.1.1.1 Basic Concepts and Principles
7.1.1.1.1 General
• If the mixture to be separated is a homogeneous, single-phase solution,
a second phase must generally be formed before separation takes place.
This is an interphase operation, which involves the transfer of mass from
one phase to another. This second phase is introduced by two methods:
Two-Phase Gas–Liquid Diffusional Operations 121

• By adding or removing energy using an energy-separating agent, for

example, in distillation
• By introducing a solvent using mass-separating agent, for example, in
absorption
• Intraphase separation, on the other hand, implies separation of components
within a phase, such as diffusion through inert barriers or membranes.
These are rate-governed operations.
• Separation of components from a liquid mixture via distillation depends
on the differences in boiling points of the individual components. Also,
depending on the concentrations of the components present, the liquid mix-
ture will have different boiling point characteristics. Therefore, distillation
processes depend on the vapor pressure characteristics of liquid mixtures.
• For separation to take place, say by distillation, the selection of an exploit-
able chemical or physical property difference is very important. Factors
influencing this are
• The physical property itself
• The magnitude of the property difference
• The amount of material to be distilled
• The relative properties of different species or components—purity
required
• The chemical behavior of the material during distillation and its
corrosiveness.
• A measure of the ease of separation of one component i from another j is
expressed by
• The relative volatility, defined as

(y i / x i ) K i
a= =
(y j / x j ) K j

where
α is the relative volatility of the more volatile component i to the less
volatile j
yi is the vapor–liquid equilibrium concentration of component i in
the vapor phase
xi is the vapor–liquid equilibrium concentration of component i in
the liquid phase
yj is the vapor–liquid equilibrium concentration of component j in
the vapor phase
xj is the vapor–liquid equilibrium concentration of component j in
the liquid phase
yi/xi = K is commonly called the K value or vapor–liquid distribu-
tion ratio of a component i

Thus, if the relative volatility between two components is very close to

one, it is an indication that it will be difficult to separate the two com-
ponents via distillation.
122 Chemical Engineering Primer with Computer Applications

• The separation factor, SF = [(Ci /C j )Top Product ]/[(Ci /C j )Bottom Product ]

where C is the concentration of a component. High value of SF means
an easy separation. A good example is the separation of salt from sea-
water by evaporation. Here, the value of SF is found, by intuition, to
be infinity, because we are separating water (volatile component) from
salt (nonvolatile).
• Net mass transfer between phases can occur only as long as driving force,
such as a concentration difference, exists between the phases.
• The principal function of equipment used for mass transfer operations is to
allow for efficient contact between the phases. Finite-stage contactors (plate
columns) and continuous contactors (packed columns) are typically used.
• Different types of distillation methods are as shown next:

Classification of distillation methods

Fractional
Single
distillation
stage
(rectification)

Simple2 Simple
Flash1 steam
(batch)
(equilibrium) distillation
differential
1 Vapors are kept in intimate contact with the liquid.
2 Vapors are withdrawn as quickly as they are formed to be condensed by a condenser.

• A stage in distillation column may be defined as a unit of equipment in

which two dissimilar phases are brought into intimate contact with each
other and then are separated. The contact allows for the diffusing compo-
nents of the feed mixture to redistribute themselves between the phases.
It is said that the resultant two phases have approached equilibrium.
• In an equilibrium stage, on the other hand, the two phases are well mixed
to allow for the establishment of thermodynamic equilibrium between the
phases leaving the stage, that is, Vn is in equilibrium with Ln for stage n as
shown in the next diagram (notice that the arrows drawn for both streams
belong to tray n). At equilibrium stage, no further change in composition
of the phases occurs at a given operating conditions. To prove this concept,
take the streams Vn and Ln and let them mix again for some time; examine
the composition of the streams leaving. If no change is observed, then tray
is named an equilibrium stage, or theoretical stage.
Ln–1 Vn

Tray n

Ln Vn+1
Two-Phase Gas–Liquid Diffusional Operations 123

7.1.1.1.2 Design Aspects

• There are two main factors that govern the design of equipment in diffu-
sional operations:
• The thermodynamic equilibrium distribution of the components
between the phases
• The rate of movement, diffusion rate, from one phase to the other
• A study of the overall assembly for finite-stage contactors is best made on
the basis of the flow and mass transfer characteristics in each individual
stage. Thus, for plate columns, each plate is considered a separate entity.
The overall design requires an analysis of the stepwise operation in the col-
umn from tray to tray. In a differential-stage contactors (packed columns)
on the other hand, the contacting operation is considered as occurring con-
tinuously throughout the column. It is a continuous contact operation.
• The main factors to be considered in the design of finite-stage columns,
other than calculating the number of the theoretical stages (plates) required
for a given separation are the following:
• Column diameter
• Tray efficiency
• Pressure drop across the tray
• The number of plates in a column is a function of the degree of separation
required, that is,

N = f (separation)

On the other hand, the diameter of a column is a function of the charge

input to the column or capacity, that is,

D = f (capacity )

7.1.2 tHree Pillars For distillation

Distillation models are based on three pillars:

• Laws of conservation of mass and energy

• The concept of ideal stage
• Raoult’s law and Henry’s law used (for ideal case) to describe the tendency
of escape for vapor/liquid at equilibrium.

The law of conservation of energy (based on first law of thermodynamics) is the

basis for the following fundamental heat balance for a distillation column. For 1 lb
of fluid flowing through a distillation system,

DH + DK.E. + DP.E. = Q - Ws

Usually in distillation, ΔK.E. and ΔP.E. are negligible. Therefore,

DH = Q
124 Chemical Engineering Primer with Computer Applications

This means that the change in enthalpy (Hout – Hin) of 1 lb of mass flowing is equal
to the heat exchanged by the system, per 1 lb of mass flowing.
A heat balance around the distillation column gives

Heat in = Heat out

Fh F + Q R = DH D + BH B + Q C

Rearranging the equation gives

Q R - Q C = [ DH D + BH B ] - FH F

Q net = enthalpy of products - enthalpy of feed

or

Q net = DH

where
∆H is the enthalpy change
ΔK.E. is the change in kinetic energy
ΔP.E. is the potential energy change
Q is the heat added to the system
Ws is the shaft work done by the system.

QC

D
F

QR

7.1.3 Features oF distillation units

In this section, we introduce to the readers some descriptive features of the distil-
lation units. An industrial distillation column consists of a set of trays (plates). It is
classified into two sections, known as the rectification and stripping sections. The
product leaving the top of the column is called the overhead product (distillate).
Distillate product may be liquid or vapor (or occasionally both) depending on the
type of condenser used, while the product leaving the bottom of the column is called
the bottom product. Figure 7.1 illustrates some of these features.
Two-Phase Gas–Liquid Diffusional Operations 125

Condenser

Reflux
Cooling water drum

Reflux

Pump
Overhead
Distillation column

product

Feed

Distillation plate
Vapor
Reboiler

Steam
Condensate
Bottoms
Bottoms product
liquid

Upflowing vapor
Downflowing liquid

FIGURE 7.1 Schematic diagram of a distillation column.

7.1.3.1 Types of Distillation Columns

Distillation columns can be classified according to five criteria: function to be car-
ried out, number of components in the feed, number of streams of products, design
pressure in the column, and column internals as shown in Figure 7.2.

7.1.3.2 Overhead Condensers

There are two main categories of condenser and they differ in function by the extent
of condensation:
1. A total condenser, where the entire vapor leaving the top of the col-
umn is condensed. Consequently, the composition of the vapor leaving
the top tray y1 is the same as that of the liquid distillate product and
reflux, x D.
2. A partial condenser, where the vapor is only partially liquefied. The
liquid produced is returned to the column as liquid, and a vapor
product stream is removed. The compositions of these three streams
126 Chemical Engineering Primer with Computer Applications

Columns
classification

Function

Number of
Flash Stage components
(equilibrium)

Batch
Binary Multi

Number of
streams Design
pressure
Two Side
streams streams

Atmospheric Under P

Vacuum

Column
internals
Bubble cap

Valve Tray Packed

Sieve

FIGURE 7.2 Classification of distillation by types of columns.

(V1, D, and R) are different. Normally, D (composition yD) is in equilib-

rium with R (composition x D).

Total condenser y1 xD

A partial condenser functions as an equilibrium separation stage, so columns with a

partial condenser effectively have an extra ideal stage.

7.1.3.3 Reflux and Reflux Ratio: Top of Column

Reflux refers to the portion of the overhead liquid product returned to the upper
part of the tower. The liquid reflux provides cooling and partial condensation of
Two-Phase Gas–Liquid Diffusional Operations 127

Vapor
Steam

Bottoms

FIGURE 7.3 Schematic of kettle-type reboiler.

the upflowing vapors, thereby increasing the efficacy of the distillation tower. The
reflux ratio is an important parameter in column operation. It is normally defined as
the ratio of reflux to distillate (L/D).

7.1.3.4 Reboilers: Bottom of Column

A reboiler can be regarded as heat exchangers that are required to transfer enough
energy to bring the liquid at the bottom of the column to boiling point, as shown in
Figure 7.3. Most reboilers are partial reboilers, since they only vaporize part of the
liquid in the column base. Partial reboilers also provide an ideal separation stage.
The balance of heating with a reboiler at the bottom of a column and cooling by
condensed reflux at the top of the column maintains a temperature gradient along
the height of the column.

7.1.3.5 Rectification and Stripping Sections in Distillation Columns

In the rectification section, vapors are enriched by removing heavy components by
reflux from top, while in the stripping section, liquid stream is stripped out of light
components by the uprising stripping stream or by the reboiler vapor output.

7.1.3.6 Effect of Operating Pressure

One of the primary considerations for operating pressure is the cooling medium
available for the reflux condenser. The overhead product will be at bubble point
conditions for a liquid product or at dew point conditions for a vapor product. These
conditions are fixed by two factors:

• The desired component separation

• The temperature of the cooling medium

The cooling media typically used are air, water, and refrigerant.
Air cooling is the least expensive. With cooling water, process temperatures of
95°F–125°F are possible. Below 95°F, mechanical refrigeration must be used to
achieve the desired condensing temperature. It is the most expensive method.
128 Chemical Engineering Primer with Computer Applications

TABLE 7.1
Types and Features of Distillation Operations
Atmospheric Vacuum
Operation Features Distillation Distillation Pressure Distillation
Application Fractionation of crude Fractionation of Fractionation and/or
oils heavy residues separation of light
(fuel oil) hydrocarbons
Justification Always work near To avoid thermal To allow condensation of
atmospheric pressure decomposition the overhead stream
using cooling water
Extra equipment Steam jet ejectors Stronger thickness for the
(as compared with and condensers vessel shell
atmospheric distillation) to produce and
maintain vacuum
Extra design features Larger diameter Increased number of trays
(as compared with because of higher (N) because separation
atmospheric distillation) vapor flow rate becomes more difficult;
increased reflux ratio

Generally, it is desirable to operate at the lowest pressure possible to maximize

relative volatility between the key components of the separation. However, if reduc-
ing the pressure requires a more expensive method, then it is not a desirable choice.
Let us review next the types of operating distillation columns with respect to the
operating (design) pressure, as illustrated in Table 7.1.

Solved Example 7.1

Propylene is to be separated from 1-butene by distillation into a distillate vapor;

90 mol% propylene. Calculate the column operating pressure assuming that the
exit temperature from the partial condenser is 100°F, the minimum attainable with
cooling water. Calculate the composition of the liquid reflux.
Solution
The operating pressure corresponds to dew point conditions for the vapor distilla-
tion conditions. Therefore, the composition of the reflux corresponds to the liquid
in equilibrium with the vapor distillate at its dew point. At the dew point,

å yi
å xi = = 1.0
Ki

Thus, the DP is a function of the Ki values, that is, DP = f(å yi /Ki ) and [(å yi /Ki ) - 1]
goes to zero at the DP.
Since Ki is a function of the operating pressure, P, we can say that

æ å yi ö
f(P) = ç ÷ -1
è Ki ø
Two-Phase Gas–Liquid Diffusional Operations 129

The method of false position (FP) will be used to perform the iterative calculations.
Now, we can say that

ì (Pk +1 – P(k ) ) ü
Pk + 2 = Pk -1 – f(Pk +1) ´ í k +1 k ý
î[f(P ) – f(P )] þ

To initialize calculations by the FP, two values are assumed for P: 100 and 190 psia.
As an example, calculations at 100 psia are done:

é æ å y i ö ù é æ 0 .9 ö æ 0 . 1 ö ù
f(P) = êç ÷ - 1ú = êç . ÷ + ç 0.675 ÷ ú – 1.0 = -0.395
ëè Ki ø û ëè 197 ø è øû

where, 1.97 and 0.675 are the k values for propylene and 1-butene at 100 psia,
respectively.
Similar iteration for next trial at P = 190 psia would lead to better values of P.
The very final result will give an operating pressure of about 186 psia for the con-
denser outlet. At this pressure, the k values of propylene and 1-butene are 1.178
and 0.424, respectively.
The liquid composition consists of 0.764 propylene and 0.236 1-butene.

7.1.4 design oF distillation columns

7.1.4.1 Introduction
Fractional distillation towers or columns are designed to achieve the required sepa-
ration efficiently. Two key factors should be considered before any design calcula-
tions can be made on a fractionation problem:

1. Operating pressure: One of the primary considerations for the operating

pressure is the cooling medium available for the reflux condenser. The over-
head product will be at the bubble point conditions for a liquid product or
at dew point conditions for a vapor product. In return, the bubble point or
the dew point pressure is fixed by a desired component separation and the
temperature of the cooling medium.
The cooling media typically used are air, water, and refrigerant. Cooling
by air is considered the least expensive. Practical exchanger design limits
the process to a 20°F approach to the ambient summer temperature. This
means that a process temperature of 115°F–125°F would apply. With cool-
ing water, process temperature of 95°F–105°F is applicable. However, for
process temperature below 95°F, refrigeration must be applied for cooling.
2. Reflux ratio and minimum number of stages (trays): The design of a frac-
tionating column could be looked upon as a capital cost versus an energy
cost trade-off issue, which is basically a function of

• The number of stages

• The reflux ratio

A distillation column can only accomplish a desired separation between the two
limits of minimum reflux (MR) and minimum number of trays, as depicted in
Figure. 7.4 Neither of these situations represents real operations.
130 Chemical Engineering Primer with Computer Applications

Condenser

Reflux drum
Enriching Reflux
(rectification)
section
Distillate
Feed

Stripping
section
Heat in
Reboiler

Heat out
Bottoms

FIGURE 7.4 Rectification and stripping sections in distillation.

Consideration of these two key factors is what we may call the process design
stage of distillation column. On the other hand, the purpose of the mechanical design
is to select the tower internals and column diameter and height. Some of the factors
involved in design calculations include feed load size and properties and the type of
distillation column utilized.

7.1.4.2 Approach to Solve Distillation Problems

There are two types of problems in distillation:

1. The design problem

• Given: The desired separation (purity)
• Find: The number of trays required in a column in order to separate a
given feed into products of desired purities
For a binary distillation, we would usually specify the mole fraction of
the more volatile component in the distillate and bottom products. The col-
umn pressure, feed flow rate, thermal condition (e.g., temperature, fraction
vapor), and composition are also specified. In addition, the (external) reflux
ratio is usually specified.
2. The rating (operational) problem
• Given: The number of trays in a column
• Find: The performance (separation)
There are a number of different types of rating problems. All of them
involve iterative (trial-and-error) solution. A guess is made of one or more
Two-Phase Gas–Liquid Diffusional Operations 131

unknown variables, and a design solution procedure is carried out using the
values guessed. The results are compared with the column specifications,
and if they do not match, a new trial is made and the solution is repeated.

7.1.4.3 Physical Models for Distillation

Two physical models are used in the design analysis of distillation columns:

Model (1) Model (2)

T. P.
Equilibrium stage Continuous
model D.
D. contact model
C.
C.
Finite stage contactors Differential stage contactors
stage operation rate operation

1. To establish a standard for measuring the 1. In this model, equilibrium is never allowed to
performance, the ideal stage concept is be achieved between phases at any point.
introduced. The approach to equilibrium Should equilibrium occur anywhere in the
realized in any stage is defined as stage system, this will be equivalent to an ∞ number
efficiency η of trays.
2. The design of tray column would involve three 2. In the design of packed column, the efficiency
basic steps: η, is function of the transport rates of the
(1) VLE data species and the construction of the separating
(2) Calculation of Ntheor device. Ntheor is calculated by a differential
(3) Finding the value of η to calculateNact balance on the column

7.1.4.4 Calculation of Number of Trays

The initial calculations involved in column design are based on relatively simple
stoichiometric (material balance) and equilibrium relationships.
The design of a distillation column depends upon three parameters:

• The composition of the feed

• The thermal condition of the feed
• The composition of the desired products

Methods applied to calculate the number of trays for distillation columns are usually
grouped into the following categories:

Feed Recommended Solution

• Binary systems Graphical methods, for example, McCabe–Thiele
• Multicomponent mixtures Shortcut methods
• Complex mixtures (petroleum hydrocarbons) Rules of thumb (empirical)
132 Chemical Engineering Primer with Computer Applications

7.1.5 mccaBe–tHiele metHod

7.1.5.1 Introduction
The method is basically a graphical design technique for stagewise contactors. Its
utility stems from the fact that the design involves the simultaneous solution of
equilibrium relationships (VLE) and the operating line to determine the number
of theoretical stages (trays) required to achieve a desired degree of separation. It is
a simplified method of analysis making use of several assumptions, yet it is a very
useful tool for the understanding of distillation operation. The VLE data must be
available at the operating pressure of the column.
The information required is the feed condition (temperature, composition), distil-
late and bottom compositions, and the reflux ratio. Detailed procedure and solved
example are given next.

7.1.5.2 Assumptions
• Constant molar overflow.
• Molar heat of vaporization of the components is roughly the same.

7.1.5.3 Procedure
1. The equation of the operating line for the rectification section is derived by
making a material balance on two passing streams on a tray, above the feed.

æ L ö æDö
y = ç ÷ x+ ç ÷ x D
èVø èVø
é R ù é 1 ù
=ê ú x + ê (R +1) ú x D
ë ( R +1) û ë û

where
y is the mole fraction of the more volatile component in the vapor phase
x is the mole fraction of the more volatile component in the liquid phase
xD is the mole fraction of the more volatile component in the distillate
D is the distillate product
L is the flow rate of liquid stream in the rectifying section
V is the flow rate of vapor stream in the rectifying section
R is the reflux ratio L/D

This is an equation of straight line, which is drawn as follows. The desired

top product composition is located on the VLE diagram on the x-axis, and a
vertical line is drawn until it intersects the diagonal line. A line with slope =
R/(R + 1) is then drawn from this intersection point as shown in the diagram
later (Figure 7.5).
Two-Phase Gas–Liquid Diffusional Operations 133

1.0

0.8 6

5
0.6
Vapor (y)

0.4 3

2
0.2
1
xF
0.0
0.0 xb 0.2 0.4 0.6 0.8 xD 1.0
Liquid (x)

FIGURE 7.5 McCabe–Thiele diagrams for calculating N.

2. The equation of the operating line for the stripping section is derived using
a similar approach for a tray below the feed.

æLö æBö
y = ç ÷ x – ç ÷ xB
èVø èVø

where
y is the mole fraction of the more volatile component in the vapor phase
x is the mole fraction of the more volatile component in the liquid phase
xB is the mole fraction of the more volatile component in the bottom
product
B is the bottom product
L is the flow rate of liquid stream in the rectifying section
V is the flow rate of vapor stream in the rectifying section

The operating line for the stripping section is then drawn in a similar man-
ner. Here, the starting point is the desired bottom product composition.
A vertical line is drawn from this point to the diagonal line, and a line of
slope L/V is drawn.
3. Given the operating lines for both the stripping and the rectification sec-
tions, the graphical construction of the steps is applied. In this way, we
count the number of steps as shown in the diagram. This particular example
shows that the seven theoretical stages are required to achieve the desired
134 Chemical Engineering Primer with Computer Applications

1.0
q>1

q=1
0.8 0<q<1

0.6
Vapor (y)

q=0

0.4
q<0
ZF

0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0
Liquid (x)

FIGURE 7.6 Feed q-lines.

separation. The required number of trays (as opposed to stages) is one less
than the number of stages since the graphical construction includes the con-
tribution of the reboiler in carrying out the separation.
The actual number of trays required is
N theorit
N actual =
h

where η stands for efficiency.

4. Location of the feed line (q-line) is determined by the conditions (state) of
the feed as shown next (Figure 7.6). In this example, feed is introduced on
the fourth tray.
q = 0 (saturated vapor)
q = 1 (saturated liquid)

0 < q < 1 (mix of liquid and vapor)

q > 1 (subcooled liquid)
q < 0 (superheated vapor)

7.1.5.4 Illustration of How to Use Excel to Solve a Problem

This Excel spreadsheet uses the McCabe–Thiele method to calculate the number
of theoretical stages needed for binary distillation. Binary distillation is a com-
mon unit of operation that separates two liquids (with one being more volatile
Two-Phase Gas–Liquid Diffusional Operations 135

or lighter). The concepts are encountered in many branches of chemical and

petroleum engineering.

Binary distillation with the McCabe-Thiele method

1.0
Mole fraction of lighter component in vapor phase

0.0
0.0 1.0
Mole fraction of lighter component in liquid phase

Simply enter your parameters at the top of the spreadsheet, including the

• Feed flow rate

• Mole fraction of the light component (or more volatile component) in the feed
• Mole fraction of the light component in the top product
• Mole fraction of the light component in the bottom product
• Reflux ratio
• Relative volatility of the light component
• q-line value

The spreadsheet will automatically calculate flow rates throughout the column,
the number of theoretical plates, the feed plate position, the MR ratio (from the
Underwood equation), and the minimum number of theoretical plates (from the
Fenske equation). (Microsoft Office Excel, 2007).

Example 7.2: Plate-to-Plate Calculations (case of Rectification column)

Concept
Thiel and Geddes method is used to calculate the number of trays. It involves
the simultaneous solution of equilibrium relationships (VLE) and the operating
136 Chemical Engineering Primer with Computer Applications

line, where the operating line is used to compute the composition of one of the
two streams passing each other for two consecutive plates, while the equilibrium
relationship is used to compute the composition of either the vapor or liquid
(in equilibrium) on the same plate.
This example is an oversimplified one for illustrative purposes.
Given

1. Derivation of the operating line

é R ù é 1 ù
yn+1 = ê ú Xn + ê ú XD. (7.2.1)
ë R+1û ë R + 1û

where R is the reflux ratio (RR) = L/V and XD is the composition of the
overhead product.
2. Equilibrium data

Yn
Xn = (7.2.2)
[Yn + a(1- Yn )]

Statement of the Example

Given: 40 mole/h of feed (vapor) that contains 20% hexane and 80% octane
entering the bottom plate, where D = 5 mole/h, XD = 0.9, R.R = 7, and α = 6. Find
the number of theoretical trays, N.1st: first:first
First: Numerical Solution
Steps:

1. The liquid composition leaving the partial condenser (plate num-

ber 0) is in equilibrium with the vapor (top product) and is calcu-
lated by Equation 7.2.2. Hence, Xreflux (leaving plate 0) = 0.9/.0.9 +
6(1 − 0.9) = 0.6
2. Y1 is calculated using Equation 7.2.1; substituting for R = 7, X = 0.6, and
XD = 0.9, we get Y1 = 0.637
3. Get the equilibrium composition of the liquid on the same tray, X1 =
0.226
4. Again, using Equation 7.2.1, get y2 = 0.3
5. Next, get X2 = 0.066, which is the bottom product leaving the column;
call it Xw

Finally, we make overall MB, and CMB:

(40)(0.2) = (5)(0.9) + (35)Xw Þ

Solve for Xw = 0.1

Therefore, two plates plus the condenser make a total of three theoretical
plates.
Second: Using Excel
Two-Phase Gas–Liquid Diffusional Operations 137

Example 7.3: Plate-to-Plate Calculations by Excel

(case of Stripping column)

A liquid mixture at the boiling point that consists of 70 mole% benzene and
30 mole% toluene is fed to a stripping column. Pressure is taken 1 atm. Feed rate
is 400 kg mole/h. Stripping operation is carried out to achieve a bottom product
W = 60 kg · mol/h that contains no more than 2 mole% benzene.
Solve the problem using Excel, in order to determine the number of the-
oretical trays, N, required to obtain the desired specifications of the bot-
tom product W. Use αAB relative volatility for benzene/toluene, where
a AB = KBenzene / K Toluene = PB0 / PT0 = 2.45

Solution
The number of trays required to reach a bottom product, exiting the stripping col-
umn, is found to be around 11 trays, as seen next; that corresponds to 1.9 mole%
benzene.
138 Chemical Engineering Primer with Computer Applications

7.1.5.5 Total and Minimum Reflux: Limiting Cases

In distillation analysis, separation of a pair of components can be improved by
increasing the number of stages while holding reflux constant or by increasing
the reflux flow for a given number of stages. This trade-off sets up two limiting
cases:

• Total reflux (TR) with minimum ideal stages, Nm

• MR with infinite ideal stages, N∞

The design trade-off between reflux and stages is the standard economic optimi-
zation problem chemical engineers always face: balancing the capital costs for
the number of trays versus the operating cost for the reflux to be recirculated.
A good design will operate near a cost optimum reflux ratio, as illustrated in
Figure 7.7.
The TR condition represents operation with no product removal. The overhead
vapor is condensed totally and returned as reflux. Consequently, the reflux ratio
(L/D) is infinite. The operating lines coincide with the diagonal line.
The aforementioned conditions of TR and MR can be further visualized by the
following approach (with the aid of the opposite diagrams):

Assume that D = (1–b) V and L = b V, where b is a constant, V

V
has a value between 0 and 1.0
Now, for the case of minimum reflux: D
let b = 0; L = 0 and D = V; number of plates = N∞
For the case of total reflux: L
N∞
Let b = 1; D = 0, L = V; number of plates = Nm Nm
F

B
L=0 B=0
MR TR

The MR condition, on the other hand, represents the theoretical opposite of TR—
an infinite number of ideal separation stages. In this case, the intersection of the
operating lines lies on the equilibrium curve itself.
This intersection is called a pinch point. A simple column will have two pinch
points (because there are two operating lines). The points change when the operat-
ing lines do. A pinch at the intersection of the feed line and the equilibrium curve
indicates that the column is operating at MR.

7.1.5.6 Tray Efficiency

Mass transfer limitations prevent the vapor leaving a tray from being in true
equilibrium with the liquid on the tray. The assumption we make of ideal stages
Two-Phase Gas–Liquid Diffusional Operations 139

150

Total cost = (1) + (2)

Annual cost ($1000) 120

90
Steam and cooling–water
costs (1)

60

Fixed charges on equipment (2)

30
Rm

Optimum reflux ratio

0
1.0 1.2 1.4 1.6 1.8 2.0
Reflux ratio (Lo/D)

FIGURE 7.7 Optimum reflux ratio for distillation column.

is only an approximation. The concept of efficiency is introduced to represent

the deviation from equilibrium. Two types of efficiencies are considered in our
discussion:

• Murphree efficiency is probably the most common to use. It assumes per-

fect mixing on the tray. Values between 0.6 and 0.75 are common for sieve
trays.
• Overall efficiency is the simplest choice. It is the ratio of the number of ideal
stages to the number of actual stages.

One can replace the true equilibrium curve with an effective equilibrium curve
(EEC) located between the true curve and the operating lines as shown in Figure 7.8.
In this case, the number of stages counted will be the true or actual trays.
Murphree efficiency is as indicated in the following equation:

[ Yn - Yn +1 ]
EEC =
[ Yn* - Yn +1 ]
Z1
=
Z2
140 Chemical Engineering Primer with Computer Applications

Equilibrium Effective
curve equilibrium curve
Y*n

Yn
Y*n
Yn n
z1 z2 Yn+1
Yn+1 n+1

Liquid composition, x

FIGURE 7.8 Illustration of an effective equilibrium curve.

O’Connell has correlated efficiency data for distillation columns as a function of

• Liquid viscosity (µ)

• Relative volatility of key components (α) (or gas solubility)

The results of the correlation for fractionators and absorbers are graphically pre-
sented by Peters and Timmerhaus. Approximate estimation of efficiency is done by
a number of methods as described by Van Winkle.

7.1.5.7 Stage Design and Efficiency

Following the equilibrium stage model described earlier, distillation columns are
designed to give discontinuous contact of phases in a series of stages.
A single-stage contact unit is designed to accomplish two main tasks:

1. To allow the contact of the V and L in such a manner, where the interfacial
area and time of contact are at their maximum for the stage to approach
equilibrium
2. To handle the required quantities of V and L without excessive pressure drop

The approach to equilibrium, on the other hand, is a rate factor, intimately tied up
into the rate of mass and heat transfer. A great number of possible variables con-
tribute to these rate processes, which makes the evaluation of efficiency extremely
difficult.
Therefore, once NT (Ntheor) is calculated, estimation of the efficiency is carried out
to find NA (Nact) rather than taking the rate processes to evaluate the efficiency as
indicated in Figure 7.9a.
In other words, to determine NA, one can pursue one of the two options:

1. The one described in Figure 7.9a

2. Head-on route, illustrated by the next diagram (Figure 7.9b)
Two-Phase Gas–Liquid Diffusional Operations 141

Calculation of NT

Find the efficiency in

order to calculate NA

If equilibrium is reached on a tray, efficiency of

contact stage would be 100%. However, since this is
a function of the rate operations of mass and heat
transfer, it is impossible for true equilibrium to be
reached. This would require ∞ area or ∞ time of
contact of the phases, or both.

Go to

Obtain
data on
efficiency

Calculate NA
= NT/E

(a)

Face complex
problems of HT.
Head on approach and M. transfer Find
Start on the trays rates?

Use ideal Flow of

stage knowledge?

NT Find E NA

(b)

FIGURE 7.9 (a) Approach to find efficiency. (b) Head on approach to find the effi-
ciency (N T, NA, and E are theoretical number of trays, actual number, and tray efficiency,
respectively).
142 Chemical Engineering Primer with Computer Applications

7.1.6 sHortcut metHods: Fenske–underwood –gilliland

7.1.6.1 Introduction
There are many so-called shortcut calculation methods for designing industrial
distillation columns. The most commonly used one is the Fenske–Underwood–
Gilliland method.

• The Fenske equation estimates the minimum number of theoretical plates

or equilibrium stages at total reflux.
• The Underwood equation estimates the MR for an infinite number of theo-
retical equilibrium stages.
• The Gilliland method then uses Fenske’s minimum plates and
Underwood’s MR to estimate the theoretical plates for a given distillation
at a chosen reflux.

Shortcut calculations provided by the Fenske–Underwood–Gilliland are most effec-

tive for a preliminary design before the use of distillation simulation software that
utilizes much more rigorous calculation methods.

7.1.6.2 Fenske Equation

log éë(X d / (1 - X d ))((1 - X b ) /X b ) ùû
N=
log aavg

where
N is the minimum number of theoretical plates required at TR (of which the
reboiler is one)
Xd is the mole fraction of the more volatile component in the overhead distillate
Xb is the mole fraction of the more volatile component in the bottom products
αavg is the average relative volatility of the more volatile component to the less
volatile component

7.1.6.3 Underwood Equation

It is represented by two relationships:

1. First equation

(a1 )(z F1 ) (a 2 )(z F 2 )

+ + = 1- q
[(a1 ) - q] [(a 2 ) - q]

where
zF is the mole fraction of component n, in the feed
q is the thermal condition of feed (heat required to vaporize 1 mol of
feed divided by molar latent heat of feed)
Two-Phase Gas–Liquid Diffusional Operations 143

2. Second equation
(a1 )(x D1 ) (a 2 )(x D 2 )
Rm + 1 = + +
[(a1 ) - q] [(a 2 ) - q]

where XD is the mole fraction of component n, in the distillate.

The first equation is solved for the value of the θ, which lies between the relative
volatilities of the key components.
Having obtained θ, we calculate Rm from the second equation.

7.1.6.4 Gilliland’s Method

Gilliland used an empirical correlation to calculate the final number of stage N,
using the diagram (Figure 7.10) as follows:
From the values calculated through the Fenske and Underwood equations
(Nmin, R, Rmin), where R is set to 1.5Rm, one enters the diagram with the abscissa
value [R – Rm]/[R + 1], which is known, and reads the ordinate of the correspond-
ing point on the Gilliland curve. The only unknown of the ordinate is the number of
theoretical stages.

Infinite
1.0
stages

0.8

0.6
N – Nmin
N+1

0.4

0.2

Min 0
stages 0 0.2 0.4 0.6 0.8 1.0
Min R – Rmin Total
reflux reflux
R+1

FIGURE 7.10 Gilliland correlation.

144 Chemical Engineering Primer with Computer Applications

7.1.7 column diameter

A fractionating tower must have sufficient cross-sectional area to handle the rising
vapors without excessive carry-over of liquid from tray to tray. The maximum allow-
able vapor velocity, Vm applicable for any specific location in the column is given by
Souders and Brown as follows:

[ L -  V ]
Vm = K v
L

An alternative form of this equation, in terms of mass velocity is

[r L - r v ]
G m = Vmrv = K v
rL

where
Vm is the maximum allowable vapor velocity, based on cross-sectional area of
empty tower, ft/s
Kv is the an empirical constant, ft/s. It is a major function of tray spacing
ρL and ρv are the liquid and vapor densities, lb/ft3, respectively
Gm is the maximum allowable mass velocity of vapor, lb/(s) · (ft2)

The total vapor load in the column

Q (lb/s) = Vm (ft/s)  V (lb/ft 3 ) A (ft 2 )

Solving the equation for the cross-sectional area A, the tower diameter is readily
obtained.

7.1.8 FlasH distillation

The problem of separating the gas from crude oil for well fluids (crude oil mixtures)
breaks down to the well-known problem of flashing a partially vaporized feed mix-
ture into two streams: vapor and liquid. In the first case, we use a gas–oil separator;
in the second case, we use what we call a flashing column.
Under the assumption of equilibrium conditions, and knowing the composition of
the fluid stream coming into the separator and the working pressure and temperature
conditions, we could apply our current knowledge of vapor/liquid/equilibrium (flash
calculations) and calculate the vapor and liquid fractions at each stage.
A flash is a single-stage distillation in which a feed is partially vaporized to
give a vapor that is richer in the more volatile components. This is the case of
a feed heated under pressure and flashed adiabatically across a valve to a lower
pressure, the vapor being separated from the liquid residue in a flash drum. This
is the case of light liquids. Apart from the gas–oil separation problem addressed
Two-Phase Gas–Liquid Diffusional Operations 145

here, methods used in practice to produce and hence separate two-phase mix-
tures are as follows:

Initial Phase Process and Conditions

Higher-pressure liquids (light) Heat under pressure, then flash adiabatically using valve
Low-pressure liquids (heavy) Partial vaporization by heating, flash isothermally (no valve)
Gas Cool-after initial compression
Gas Expand through a valve or engine

For flashing to take place, the feed has to be two-phase mixture, that is, it satisfies
the following:
TBP < Tf < TDP (as indicated in the VLE diagram, Figure 7.11).
Or,
The sum of (ZiK i) for all components is greater than 1 and the sum of [zi/K i] for
all components is less than 1, where TBP, Tf, and TDP are the bubble point of the feed
mixture, flash temperature, and dew point of the feed mixture, respectively.
Zi and K i are the feed composition and equilibrium constant, respectively, for
component i.

Vapor

T.D.P.

Tf
Va
Temperature

po
r+
T.B.P. liq
uid

Liquid

X, feed
Concentration (mole fraction)

FIGURE 7.11 Conditions for the flashing of a binary system.

146 Chemical Engineering Primer with Computer Applications

7.1.8.1 Flash Equation

The need to discuss flash calculation arises from the fact that it provides a tool to
determine the relative amounts of the separation products V(gas) and L(oil) and their
composition Yi and Xi, respectively.
The flash equation is derived by component material balance Fzi = Vyi + Lxi, as
presented in Figure 7.12.
Two forms for the flash equation are presented:

1. Simple form

Zi
Xi =
1 - (V/F )(1 - K i )

For given conditions of P and T, the solution of the equation to find the value
of Xi is obtained by trial and error assuming a value for V/F (take F unity),
until the sum of [Xi] = 1 is satisfied.
2. Functional form

i =c
é ù
å êë1 - g(1 - K ) úû - 1
Zi
f (g ) =
i =1 i

where g = V/F. The desired root to this function, gr = (V/F)r, is the value
that makes the function f(g) go to zero or the sum of [Xi] = 1. The solution
of this flash equation is carried out using computers. Details on using func-
tional technique are fully described in many references.

V, Yi

F, Zi

L, Xi

FIGURE 7.12 Flash separation of binary mixture.

Two-Phase Gas–Liquid Diffusional Operations 147

The vapor–liquid equilibrium constant, defined as

Yi
Ki =
Xi

where
Yi is the mole fraction of component i in the vapor phase
Xi is the mole fraction of component i in the liquid phase
K i is the equilibrium constant of component i for a given T and P, is considered
the key concept used in the computation of phase behavior of hydrocarbon
mixtures in oil and gas streams

K is called the distribution constant because it predicts the distribution of a compo-

nent in each phase: vapor and liquid. K is a function of T, P, and the composition of
a given system. The K values most widely used are those developed by the National
Gas Processors Association. Because the K values are designated for a specific con-
vergence pressure (defined as the pressure at a given T, where the values of K for all
component in a system become or tend to become equal to unity), it is important that
the value of the operating pressure of the system should be below the convergence
pressure used in predicting the K values.

7.1.9 reactive distillation

Reactive distillation is a process where the chemical reactor is also the still.
Separation of the product from the reaction mixture does not need a separate distil-
lation step, which saves energy (for heating) and materials. A case study on reactive
distillation (on the production of methyl acetate) is presented in Chapter 10. It is a
manifestation of the merits of reactive distillation.

7.2 PART II: ABSORPTION AND STRIPPING

Absorption is the transfer of a solute component in a gas-phase stream into a liquid
absorbent (solvent). The objective in absorption is to bring a gas stream into direct
contact with a liquid solvent to enable soluble components of the gas to be washed
out by the solvent. Absorption finds applications in two main fields:

• The recovery of valuable components from a gas stream

• The removal of obnoxious materials or components from a gas stream

Stripping (desorption) on the other hand, is the transfer of gas, dissolved in a liquid,
into a gas stream. It is the reverse of absorption. The fluid to be processed is liquid;
148 Chemical Engineering Primer with Computer Applications

the aim is to liberate a dissolved gas from the fluid. Stripping can be carried out by
more than one option:

• Using a stream of inert gas

• Applying a temperature rise by heating and boiling of solutions
• Applying pressure reduction

Design methods for absorbers are presented. This includes graphical technique,
numerical (analytical) approach, and the unit concept method.

Contact between
gas and liquid
Stripping is the phases is brought A Typical example is
removal of a solute washing of ammonia
by two means: from a mixture of
from a liquid by
(ammonia+air) by
using heat or inert
liquid water
Gravity Mech.

Absorption is a process in Absorption is a process in

which molecules transfer which a soluble gas is
Definition and basic concepts
from a gas phase into absorbed from its mixture
liquid a phase with an inert gas by means
Absorption
of a liquid
and
stripping

Solution of
Absorption Design aspects design problems
tskes place by is reached by:
using:

Graphical
methods
Plate Packed Spray
columns towers columns
Analytical
methods

The diameter of packed tower

Chemical and
depends on: Transfer
physical solvents are
the most commonly 1. Quantities of gas and liquid unit
used absorption 2. Their properties concept
processes for acid 3. Ratio of one stream to
gas treatment the other.

7.2.1 Basic concePts

Absorption depends on intimate contact of gas and liquid phases under favorable
conditions. Contact is achieved by maximizing the interfacial area of surfaces of gas
and/or liquid to each other. This is achieved by two approaches:
Two-Phase Gas–Liquid Diffusional Operations 149

The action of gravity (buoyancy) Mechanical means or devices

of the fluid by using: by using:

(a) Plate towers (a) Spray columns

Breaking the gas into little bubbles passing Breaking the liquid into tiny drops
through a volume of liquid. dispersed through a volume of gas.
(b) Packed columns (b) Centrifugal absorbers
Breaking the liquid into multiplicity of slow-flowing films, which forms and reforms
through a volume of gas.
(c) Wetted-wall columns
The general features of absorption and stripping operations are illustrated as follows:
Absorption: Removal of c2+ from natural gas Stripping: Removal of light hydrocarbons
using n-Octane (lean O) from heavy cuts by heating or using inert.
Lean gas
Lean oil Rich gas
Rich oil

Lean oil
Lean gas
Rich gas Rich oil

7.2.2 outline oF design aPProacH

Solution of design problems in absorption is reached by one of the following methods:

1. Graphical methods
2. Analytical methods using absorption factors
3. Transfer unit concept

The following parameters are the most important to consider in the design of
absorbers/strippers:

• The best solvent to use

• The optimum gas velocity through the absorber, hence the vessel diameter
• The height of the vessel and its internal members or the number of contact-
ing trays
• The optimum solvent circulation rate through the absorber and stripper
• Temperatures of streams entering and leaving the absorber and stripper,
and the quantity of heat removed
• Operating pressures at which absorption process takes place
150 Chemical Engineering Primer with Computer Applications

7.2.3 graPHical metHods: solution For simPle

countercurrent aBsorPtion oPerations
The most generally satisfactory methods of determining the number of ideal stages
in a cascade are graphical ones. Similar to distillation, the graphical determination
of the number of stages in absorption involves the alternate use of the operating line
and the equilibrium curve as shown in Figure 7.13a. When the solute is being trans-
ferred from the liquid phase, L, to the vapor phase, V, the process is called stripping.
This is case 7.13b.
The operating line could be plotted by either of the two options:

• By knowing all four of the compositions at both ends of the column

• By knowing three compositions and the slope L/V of the operating line

In absorption problems, there are two carriers and a solute which is partitioned
between them. An example is the use of sulfuric acid to absorb humidity (water)
from moist air. The two carriers are: air and acid, where water is the solute. This is
represented by

Moist
air Water Acid

Other absorption problems involve the use of nonvolatile solvents. An example

is the scrubbing of benzene/air mixture using a nonvolatile hydrocarbon oil as
solvent.

Equilibrium
(Tower bottom) line
y1

(Top)
Mole fraction, y

y2
Operating
line

Equilibrium
line
y2 Operating
(Top) line
y1 (Tower bottom)
0 0
0 x2 x1 0 x1 x2

(a) Mole fraction, x (b) Mole fraction, x

FIGURE 7.13 Illustrations for the operating line and equilibrium curve for absorbers/
strippers. (a) Case of absorption. (b) Case of stripping.
Two-Phase Gas–Liquid Diffusional Operations 151

7.2.4 material Balance calculations

In the absorber, shown in Figure 7.14, we have two streams flowing countercurrent
under the following conditions:

1. The gas stream flow rate G (mol/h), at any point in the tower consists of two
components:
a. Diffusing solute, A, composition y, or Y = y/(1 − y) and GA = G · y; and
b. Nondiffusing (inert gas), composition is (1 − y); Vs = V(1 − y) and (Vs +
VA) = [V(1 − y) + V · y] = V
2. The liquid stream, L mole/h · ft2, at any point, is composed of two species:
a. Nonvolatile liquid, Ls
b. The absorbed solute of the gas, in the liquid phase, having mole frac-
tion: X = x/(1 − x) and Ls = L(1 − x), LA = Lx

Since Vs and Ls are almost constant in quantity, as they pass through the tower, it is
convenient to express the material balance in terms of these flow rates.
Solute balance around the boundary shown in the diagram yields

Vs (Y1 - Y) = L s (X1 - X)
This represents an equation of straight line (operating line):

Y1 – Y =[Ls/Vs] X2 – X , or

Where, at the terminal conditions: Y Y2 and X X1

where
Y is the moles of solute/moles of inert gas
X is the moles of solute/moles of inert liquid

Finally, we obtain
L [y b - ya ]
=
V [x b - xa ]

V2, y2, Y2 b (top)

L2, x2, X2

Y X

V1, y1, Y1 a (bottom)

L1, x1, X1

FIGURE 7.14 Material balance for an absorber.

152 Chemical Engineering Primer with Computer Applications

Example 7.4

Moist air that enters is to be dried in a countercurrent drier using sulfuric acid to
absorb the moisture. Conditions are as given next.
Given

(i) Moisture content in air is Yb = 28 × 10 −3 moles water/mol dry air.

(ii) Water content is Ya = 8 × 10 −3 after drying.
(iii) The acid introduced to the dryer has a composition of Xa = 2 moles
water/mol (H2SO4) and leaves with Xb = 9. With reference to the given
equilibrium diagram,

Find

(a) The ratio of liquid absorbent to gas treated

(b) The smallest ratio of acid to air that can be used to dry the air from point
“b” to point “a” shown in Figure 7.15

Solution
(a) As shown earlier, the slope of the operating line EF is
Y/X = ratio of: H2SO4 Acid to Air treated
= 2.86 × 10 −3, mole acid to mole dry air
= 2.86 mole acid for 1000 moles dry air
(b) Line FH has the lowest slope through F that can provide a value for Yb =
2.8 × 10 −2.

0.032
Yb E H C
ium
ilibr
Equ r ve
0.024 cu
B
Moles dry air
Moles H2O

D
P
0.016 N O
L
J M a b
H K Air, H2O Air, H2O
I
Y=

Yb = 0.028 Countercurrent Ya = 0.008

Ya Acid, Acid,
drier
0.008 G
F Xb = 9 Xa = 2

A Xa Xb
0
0 4 8 12 16 20
Moles H2O
X=
Moles H2SO4

FIGURE 7.15 Graphical solution of Example 7.4.

Two-Phase Gas–Liquid Diffusional Operations 153

This line is a tangent to the equilibrium curve at point D. It has a slope of 1.64 ×
10 −3 mol acid per mole air. Although this is the smallest amount of acid to be used,
it requires an infinite number of stages as shown in the diagram (pinch point).

Example 7.5

Using nonvolatile hydrocarbon oil as a solvent, benzene/air mixture is to be

scrubbed using a simple countercurrent absorption column. Data are shown in
Figure 7.16.
Given

• Inlet feed gas contains 5% benzene.

• Flow rate of feed gas is 600 lb moles/h.
• Solubility of benzene in oil follows Raoult’s law.
• The average molecular weight of oil is 200.
• Tower operates isothermally at 80°F and a pressure of 1 atm.

Find

(a) The minimum oil rate (lb/h) required to recover 90% of the entering benzene
(b) The number of theoretical stages needed if an oil rate that is 1.5 times the
minimum is used.

(XN, YN+1)actual (XN, YN+1)min L/V

0.05

0.04
Ya, lb . mole benzene/lb . mole air

0.03

0.02

0.01

(X0, Y1)

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Xa, lb . mole benzene/lb . mole absorbent oil

FIGURE 7.16 Graphical solution of Example 7.5.

154 Chemical Engineering Primer with Computer Applications

Solution
First. Calculation of the equilibrium data, Ya /Xa, for benzene/air is done.
For benzene,

æP ö
Ya = ç a ÷ xa
èPø

At 80°F, Pa = 103 mm Hg and P = 760 mm Hg; therefore, ya = 0.136xa.

To assure a straight operating line, mole ratios will be used: ya = Ya /(1 + Ya) and
xa = Xa /(1 + Xa); hence, Ya /(1 + Ya) = 0.136 Xa /(1 + Xa).
Assuming values for Ya in the range from 0 to 0.05, the corresponding values
of Xa are calculated and the equilibrium data of Ya and Xa are plotted as shown in
Figure.
Inlet gas contains (0.05)(600) = 30 lb mol of benzene. Recovery of benzene
is 90%. Benzene leaving in the gas is 3 lb mole; Y1 = 3.0/570 = 0.00526 and
X0 = 0.
Conditions at the upper end (outlet) are now set and plotted. Feed condi-
tions are

0 .0 5
X 0 = 0 .0 and YN+1 = = 0.0526
0.95

hence, the operating line is drawn.

Minimum liquid rate occurs when the operating line touches the equilibrium
curve to give

æLö (0.0526 - 000526)

çV÷ = (0.52 - 0)
= 0.091
è øm

(Oil rate)m = (0.091)(570)(200) lb/h

Operating oil rate = (1.5)(Oil rate)m = 15,600 lb/h, and the value of XN = 0.345
The number of stages are figured out to be about five stages for the given oil
rate.
A detailed discussion for the design methods of plate and packed absorbers is
beyond the scope of this chapter. Reference to Perry’s Handbook (50th edition),
pp. 14-14–14-24 is recommended. Heat effects in gas absorption, multicompo-
nent systems, and absorption with chemical reaction are fully discussed as well
on pp. 14-24–14-31.

7.2.5 analytical metHods: equations to calculate tHe

numBer oF stages For aBsorBers/striPPers
As stated earlier, when the operating line and the equilibrium lines are both
straight over a given concentration range, the number of stages N can be calcu-
lated by formula (analytically), as shown next. In this case, graphical technique
Two-Phase Gas–Liquid Diffusional Operations 155

is unnecessary. The method is known as the absorption factor method. Derivation

of the absorption factor equation is detailed in McCabe and Smith. The final
derived equations are
1. For the transfer of solute “A” from vapor phase to liquid phase, that is,
absorption, the following relationship is obtained:

log{[(y b - y*b ) /(y a - y*a )]

N=
log A

When A, the absorption factor, is defined as L/mV = 1,

[y b - ya ]
N=
[ y a - y*a ]

where m is the slope of the operating line.

2. For the stripping process, when S is defined as 1/A = mL/V

[ xa - x b ]
N=
[ x b - x*b ]

These series of equations are known as Kremser equations.

Example 7.6

Ammonia is to be scrubbed from a gas containing 4% ammonia and 96% air by

volume, in a countercurrent plate column. Water containing 0.003 mole NH3 per
mole of water is used at a rate of 1.1 mole H2O per mole of air. Ninety percent of
the ammonia entering is to be scrubbed. K factor for ammonia is

= 0.8 [moleNH3 /mole air]/[moleNH3 /moleH2O].

Calculate:

(a) The exit concentration of ammonia in the liquid

(b) The number of ideal trays required

Solution
(a) Material balance based on 1 mole of air and using mole ratio units is

4
Yb = = 0.04167
96
156 Chemical Engineering Primer with Computer Applications

Ammonia absorbed = 90% [0.04167] = 0.0375 = 0.0341 mol ammonia

per mol of H2O.
Xb = 0.003 + 0.0341 = 0.0371 mole ammonia per mole of H2O.
(b) Ya = 0.00417 mole ammonia per mole of air; A = 1.1/0.8 = 1.375;
Ya* = 0.00334; and Yb* = 0.02968
Therefore,

log{[0.04167 - 0.02968]/[0.00417 - 0.00334]}

N=
log 1375
.

= 14 trays

7.2.6 transFer unit concePt For aBsorPtion in Packed columns

The following is a brief discussion for the calculation of the height of a packed
absorption tower, Z. Because of space limitation, presentation is given for the case of
transfer unit based on gas film:

Z = (H G )(N G )

where
HG is the height of a transfer unit based on the gas film. The units of H are in
meter
NG is the number of transfer units

When the solutions in gas absorption are dilute (concentrations < 10%), the following
equation is applicable:

é (1 - y)LM ù é (y1 - y 2 ) ù
Z = HGNG = HG ê ú ê ú
ë (1 - y) û av ë (y - y i ) û

where
y1 and y2 are the mole fractions of component A in gas inlet and gas outlet,
respectively
y and yi are the mole fraction in bulk of gas phase and at gas side of interface,
respectively

7.2.7 role oF aBsorPtion in natural gas Field Processing

Natural gas associated with crude oil production or produced from gas fields gener-
ally contains undesirable components such as H2S, CO2, N2, and water vapor. Field
processing of natural gas implies the removal of such undesirable components before
the gas can be marketed.
Two-Phase Gas–Liquid Diffusional Operations 157

Acid gas (H2S and CO2)

to sulfur recovery
Sweet gas
Treated gas
to NGL
recovery
Amine
Amine regenerator
Slug absorber Cooler
Sour gas catcher
from GOSP Food gas
compressor
Sour condenser Rich DGA
from GOSP (W/H2S) Lane DGA
(W/H2S)
Condenser
stripper

Sweet NGL
to pipeline
shipping
Cooler

FIGURE 7.17 Separation of natural gas liquid by absorption.

Chemical and physical solvents are the most commonly used absorption pro-
cesses for acid gas treatment. In the chemical process, mono- and diethanolamine
are used to react with the acid gases reversibly and form products that can be gener-
ated by a change in temperature as given in Figure 7.16 The physical process, on
the other hand, uses a solvent to absorb the sour gases (Sulfinol process) from the
natural gas. The absorbed impurities are then separated from the rich solvent by
steam stripping.
Another important application for gas absorption is the separation of the com-
ponents of natural gas liquid, known as C2+, ethane and heavier. This is done using
heavy hydrocarbon cut to absorb these components, which are generated from the
rich solvent by distillation, as shown in Figure 7.17.

END-OF-CHAPTER SOLVED EXAMPLES

Example 7.7

For the following distillation column, write a code to find the value of stream B and
the compositions of stream B.
158 Chemical Engineering Primer with Computer Applications

Ptop = 6.5 kPa

CW
30°C 40°C

60 kmole/h D = 2 kg/h Distillate

Td = 47°C
Feed Water (waterD) 3.629%
Tf = 90°C F Acetic acid (aceticD) 96.183%
Pf = 19 kPa Acrylic acid (acrylicD) 0.188%
92.4 = kg/h
Water 0.216%
Acetic acid 5.736% LPS
Acrylic acid 94.048% 160°C

Pbot = 15.8 kPa B Bottom

Tb = 89°C
Acetic acid (aceticB) %?
Acrylic acid (acrylicB) %?
Solution Water (waterB) %?

MATLAB®
Results
Two-Phase Gas–Liquid Diffusional Operations 159

Example 7.8

Xylene, styrene, toluene, and benzene are to be separated with the array of distilla-
tion columns that are shown later. Write a program to calculate the amount of the
streams D, B, D1, B1, D2, and B2 and also to calculate the composition of streams
D and B.

7% xylene
D1
4% styrene
54% toluene
35% benzene
#2

18% xylene
B1 24% styrene
#1 42% toluene
15% xylene 16% benzene
25% styrene
40% toluene
15% xylene
20% benzene D2 10% styrene
54% toluene
F = 70 moles/min
21% benzene

#3
B

B2 24% xylene
65% styrene
10% toluene
1% benzene

Solution
Making material balances on individual components on the overall separation
train yields the following equation set:
Xylene: 0.07D1 + 0.18B1 + 0.15D2 + 0.24B2 = 0.15 × 70
Styrene: 0.04D1 + 0.24B1 + 0.10D2 + 0.65B2 = 0.25 × 70
Toluene: 0.54D1 + 0.42B1 + 0.54D2 + 0.10B2 = 0.40 × 70
Benzene: 0.35D1 + 0.16B1 + 0.21D2 + 0.01B2 = 0.20 × 70
Overall material balances and individual component balances on column 2 can
be used to determine the molar flow rate and mole fractions from the equation of
stream D.
Molar flow rates: D = D1 + B1
Xylene: XDxD = 0.07D1 + 0.18B1
Styrene: XDsD = 0.04D1 + 0.24B1
Toluene: XDtD = 0.54D1 + 0.42B1
Benzene: XDbD = 0.35D1 + 0.16B1
160 Chemical Engineering Primer with Computer Applications

where
XDx is the mole fraction of xylene
XDs is the mole fraction of styrene
XDt is the mole fraction of toluene
XDb is the mole fraction of benzene
Similarly, overall balances and individual component balances on column 3 can
be used to determine the molar flow rate and mole fractions of stream B from the
equation set.
Molar flow rates: B = D2 + B2
Xylene: XBxB = 0.15D2 + 0.24B2
Styrene: XBsB = 0.10D2 + 0.65B2
Toluene: XBtB = 0.54D2 + 0.10B2
Benzene: XBbB = 0.21D2 + 0.01B2
where F, D, B, D1, B1, D2, and B2 are the molar flow rates in mole/min.
Solution
clear all and clc
A =[0.07,.
0 18,.0 15,.
0 24; 0.040
,.240,.10,.
0 65;0.540,.420,.540
,0.1;0.35,.
0 160 0 01];
,.21,.
B=[0.15*70; 0.25*70; 0.4*70; 0.2*70];
X = A\B; D1 = X(1),B1 = X(2),D2= X(3),B2= X(4), D = D1+B1
B = D2+B2
XDx =(.07*D1+.18*B1)/D XDs =(.04*D1+.24*B1)/D
XDt =(.54*D1+.42*B1)/D XDb =(.35*D1+.16*B1)/D
XBx =(.15*D2+.24*B2)/B XBs =(.1*D2+.65*B2)/B
XBt =(.54*D2+.1*B2)/B XBb =(.21*D2+.01*B2)/B

The results will be

D1 = 26.2500
B1 = 17.5000
D2 = 8.7500
B2 = 17.5000
D = 43.7500
B = 26.2500
XDx = 0.1140
XDs = 0.1200
XDt = 0.4920
XDb = 0.2740
XBx = 0.2100
XBs = 0.4667
XBt = 0.2467
XBb = 0.0767

Example 7.9

For the following separation system, we know the inlet mass flow rate (in kg/h) and
the mass fractions of each species in the inlet (stream 1) and each outlet (streams
2, 4, and 5). Calculate the unknown mass flow rates of each outlet stream.
Two-Phase Gas–Liquid Diffusional Operations 161

Solution
If we define the unknowns as x1 = F1, x2 = F2, and x3 = F3 and set up the
mass balances for the following:

1. The total mass flow rate x1 + x2 + x3 = 10

2. The mass balance on species 1
0.04x1 + 0.54x2 + 0.26x3 = 0.2*10
3. The mass balance on species 2
0.93x1 + 0.24x2 = 0.6*10

F1 = ?

A = 4%
B = 93%
C = 3%

F = 10 F2 = ?
A = 20% A = 54%
B = 60% B = 24%
C = 20% C = 22%

F3 = ?

A = 26%

then these three equations can be written in matrix form

é 1 1 1 ù é x1ù é10 ù
ê ú ê ú ê ú
ê0.04 0.54 0.26ú êx2ú = ê 2 ú
êë 0.93 0.24 0 úû êë x3úû êë 6 úû

To find the values of unknown flow rates, write the code

A = [1,1,1;.04,.54,.26;.93,.24,0]; B = [10;.2*10;.6*10];
X = AB; F1 = X(1),F2 = X(2),F3 = X(3)
The results will be
F1 = 5.8238
F2 = 2.4330
F3 = 1.7433
162 Chemical Engineering Primer with Computer Applications

Example 7.10

In an absorption tower, ammonia is absorbed from air at atmospheric pressure by

acetic acid. The flowrate of 2 kg/m2s in a test corresponds to a Reynolds number of
5100 and hence a friction factor R/pu2 of 0.020. At the temperature of absorption
the viscosity of the gas stream is 0.018 mN · s/m2, the density is 1.154 kg/m3, and
the diffusion coefficient of ammonia in air is 1.96 × 10 –5 m2/s.

a) Determine the mass transfer coefficient through the gas film in kg/m2s
(kN/m2).
b) Determine the mass transfer coefficient through the gas film in kg/m2s
(kN/m2) if the flow rate increases from 2 to 10 kg/m2s.

Solution
Given
Flow rate = 2.00 kg/m2s
Reynolds no. = 5100
Friction factor R/pu2 = 0.020
Viscosty = 0.0180 mN · s/m2
Density = 1.154 kg/m3
Diffusion coefficient = 0.000020 m2/s

(a)

[(hd/u)*(PBm/P)*(u/pD)exp0.56]=jd
(u/pD)exp0.56 = 0.88
(hd/u)*(PBm/P)= 0.02261364
u = G/p = 1.73310225
KG = [(hd/R*T)*(PBm/P)] = 1.5319E-05
KG = 0.00026392 kg/m2s (kN/m2)
KG = 2.70 × 10–4 kg/m2s (kN/m2)

(b)
The previous steps were repeated for different ammonia flow rates and
the mass transfer coefficient was calculated in each case.
The results were shown in the following table and were plotted in
the figure.

Flow Rate kg
2 0.0002
4 0.0005
6 0.0008
8 0.00107
10 0.00134
Two-Phase Gas–Liquid Diffusional Operations 163

Example 7.11

A continuous fractionating column is required to separate a mixture containing

0.695 mole fraction n-heptane (C7H16) and 0.305 mole fraction n-octane (C8H18)
into products of 99 mole % purity. The column is to operate at 101.3 kN/m2 with
a vapor velocity of 0.6 m/s. The feed is all liquid at its boiling-point, and this is
supplied to the column at 1.25 kg/s. The boiling point at the top of the column may
be taken as 372 K, and the equilibrium data are:

Mole fraction of heptane in vapor 0.96 0.91 0.83 0.74 0.65 0.50 0.37 0.24
Mole fraction of heptane in liquid 0.92 0.82 0.69 0.57 0.46 0.32 0.22 0.13

Determine the minimum reflux ratio required. What diameter column would be
required if the reflux used were twice the minimum possible?
164 Chemical Engineering Primer with Computer Applications

heptane in vapour 0.96 0.91 0.83 0.74 0.65 0.5 0.37 0.24 0
heptane in liquid 0.92 0.82 0.69 0.57 0.46 0.32 0.22 0.13 0

Xd = 0.695

: −0.475 = xD/(Rm + 1) and Rm = 1.08

If 2Rm is used, then: R = 2.16 Ln/D = 2.16

Taking 100 kmol of feed, as a basis, an overall mass balance and a balance for the

100 = (D + W)

and: 100 × 0.695 = 0.99D + 0.01W since 99 per cent n-octane is required.
Hence: D = 69.9 and W = 30.1
and: Ln = 2.16D = 151 and Vn = Ln + D = 221
The mean molecular mass of the feed = (0.695 × 100) + (0.305 × 114) =
104.3 kg/kmole.
Thus: feed rate = (1.25/104.3) = 0.0120 kmole/s
The vapor flow at the top of the column = (221/100) × 0.0120 = 0.0265 kmole/s.
The vapor density at the top of the column = (1/22.4) (273/372) =01
Hence, the volumetric vapor flow = (0.0265/0.0328) = 0.808 m3/s
If the vapor velocity = 0.6 m/s, the are a required = (0.808/0.6) = 1.35 m2 equivalent
to a column diameter of [(4 × 1.35)/π]0.5 = 1.31 m.

REFERENCE
Microsoft Office Excel 2007, Excel 2007 Win32 English VUP CD, http://excelcalculations.
blogspot.com/?, Mindspark Interactive Network, Inc., 2016.
 8 Reaction Kinetics,
Chemical Reactors,
and Thermodynamics
Chapter 8 consists of three parts: Part I “Fundamentals of Reaction Kinetics,”
Part II “Types and Design of Chemical Reactors,” and Part III “Introduction to
Thermodynamics.”
In Part I, the two forms of the rate law for chemical kinetics are presented: the
differential rate law and the integrated rate law. Most chemical reactions obey one
of the three differential rate laws:

1. Zero-order reactions (for which reaction rates are independent of

concentration)
2. First-order reactions
3. Second-order reactions

The main factors that influence the reaction rate are discussed. For each inte-
grated rate law, the characteristic plots are shown and presented in table form as
well.
A summary of the types of laboratory and industrial catalytic reactors is pre-
sented in Part II, along with the equations underlying the design of a chemical
reactor.
Part III, on the other hand, introduces thermodynamics. Thermodynamics applies
to a wide variety of topics in science and engineering, especially physical chem-
istry, chemical engineering, thermal power generation, and industrial applications
of steam and combustion turbines. It is defined as the subject that relates heat to
forces acting between contiguous parts of bodies and the relation of heat to electrical
energy.

165
166 Chemical Engineering Primer with Computer Applications

A simple rule of thumb: for every 10°C increase, the reaction rate doubles.

Forms of rate law: (i) The

Most chemical reactions obey one
Define: A rate law is a math. differential rate
of three differential rate laws:
equation that describes the law
progress of a reaction.

(ii) The integrated

rate law
The integrated Zero order First order
rate law is r=k r = k[A]
given by: Second order
2
r = k[A]

Fundamentals and Key process variables are:

–k
[A] = [A]0 e technical aspects
Residence time (τ, lower
case greek tau)
Volume (V)
Classifiction of Temperature (T)
reactors Pressure (P)
Concentrations of
chemical species
Heat transfer
coefficients (h, U)

(1) Based on models and types (2) Based on heating and cooling

Internal heat or cooled

Reactor
Into two main basic reactor
Into three models: design
vessel types: External heat or
Batch R., CSTR,
tank R. and cooled reactor
Plug flow R.
tubular R. Jacketed reactor

The rate of a chemical reaction can Capacity of the reactor V, is computed

vary from a value approaching ∞ from the specified feed rate and feed
[ionic reactions] to essentially 0. Most concentration of component A and with
reactions occur at rates between the knowledge of space time, Φ.
these two limits.

8.1 PART I: FUNDAMENTALS OF REACTION KINETICS

8.1.1 introduction
Chemical kinetics is the branch of chemistry that addresses the question: “How
fast do reactions go?” Chemical kinetics, also known as reaction kinetics, could be
described as the study of rates of chemical processes.
In this respect, chemistry can be thought of, at the simplest level, as the science
that concerns itself with making new substances from other substances.
If chemistry is making new substances out of old substances, through a chemical
reaction, then there are two basic questions that confront us and need to be resolved
ahead of any action to be taken.
Reaction Kinetics, Chemical Reactors, and Thermodynamics 167

Two
fundamental
questions?

Is the reaction feasible

How fast is this reaction?
to go? This is the subject
This is the subject of
of chemical
chemical kinetics
thermodynamics

One concludes that thermodynamics gave us a partial answer to our problem. Not
only do we have to know whether a reaction is thermodynamically favored, but we also
have to know whether the reaction can or will proceed at a finite rate. This completes the
other part of the chemistry story by the study of the rate of reactions or chemical kinetics.

8.1.2 six categories oF cHemical reactions

According to Myers (1951), all chemical reactions can be placed into one of six
categories:

1. Combustion: A combustion reaction is when oxygen combines with another

compound to form water and carbon dioxide:

CH4 + 2O2 → 2H2O + CO2.

2. Synthesis: A synthesis reaction is when two or more simple compounds

combine to form a more complicated one.
One example of a synthesis reaction is the combination of iron and sulfur
to form iron sulfide:

8 Fe + S8 ® 8 FeS

3. Decomposition: A decomposition reaction is the opposite of a synthesis

reaction—wherein a complex molecule breaks down to make simpler ones.
One example of a decomposition reaction is the electrolysis of water to
make oxygen and hydrogen gas:

2H 2 O ® 2H 2 + O 2

4. Single displacement: This is when one element trades places with another
element in a compound.
One example of a single displacement reaction is when magnesium
replaces hydrogen in water to make magnesium hydroxide and hydrogen gas:

Mg + 2H 2O ® Mg(OH)2 + H 2
168 Chemical Engineering Primer with Computer Applications

5. Double displacement: This is when the anions and cations of two different
molecules switch places, forming two entirely different compounds.
One example of a double displacement reaction is the reaction of lead
nitrate with potassium iodide to form lead iodide and potassium nitrate:

Pb(NO3 )2 + 2KI ® PbI 2 + 2KNO3

6. Acid–base reaction: This is a special kind of double displacement reaction

that takes place when an acid and base react with each other.
One example of an acid–base reaction is the reaction of hydrobromic
acid (HBr) with sodium hydroxide:

HBr + NaOH ® NaBr + H 2O

8.1.3 reaction rates

Chemical kinetics deals with the experimental determination of reaction rates from
which rate laws and rate constants are derived. In many reactions, the rate of reac-
tion changes as the reaction progresses. Initially the rate of reaction is relatively
large, while at a very long time, the rate of reaction decreases to zero (at which
point the reaction is complete). In order to characterize the kinetic behavior of a
reaction, it is desirable to determine how the rate of reaction varies as the reaction
progresses.
The main factors that influence the reaction rate include

1. The physical state of the reactants

2. The concentrations of the reactants
3. The temperature at which the reaction occurs
4. The presence of catalysts

8.1.3.1 Forms of Rate Law

A rate law is a mathematical equation that describes the progress of the reaction.
In general, rate laws must be determined experimentally. Unless a reaction is an
elementary reaction, it is not possible to predict the rate law from the overall chemi-
cal equation. There are two forms of a rate law for chemical kinetics:

1. The differential rate law

2. The integrated rate law

The differential rate law relates the rate of reaction to the concentrations of the vari-
ous species in the system. Differential rate laws can take on many different forms,
Reaction Kinetics, Chemical Reactors, and Thermodynamics 169

especially for complicated chemical reactions. However, most chemical reactions

obey one of three differential rate laws:

1. Zero-order reactions (for which reaction rates are independent of concentration)

2. First-order reactions
3. Second-order reactions

Each rate law contains a constant, k, called the rate constant. The units for the rate
constant depend upon the rate law, because the rate always has units of mole/L ⋅ s and
the concentration always has units of mole/L.
It should be stated that the rate constant, k, is dependent on the temperature of
which the reaction takes place. This can be seen through the Arrhenius equation
shown as follows:

k = Ae - E / RT

In addition to temperature, the rate constant k is dependent on the activation energy,

Ea (in Joules). “A” in the equation represents a preexponential factor that has the
same units as k. Finally, R is the universal gas constant.

8.1.3.1.1 Zero-Order Reaction

For a zero-order reaction, the rate of reaction is a constant. When the limiting reac-
tant is completely consumed, the reaction stops. The differential rate law is given by
the following equation:

r=k (8.1)

The rate constant, k, has units of mole/L · s.

8.1.3.1.2 First-Order Reaction
For a first-order reaction, the rate of reaction is directly proportional to the concentra-
tion of one of the reactants. The differential rate law is given by the following equation:

r = k[ A] (8.2)

The rate constant, k, has units of s−1.

8.1.3.1.3 Second-Order Reaction
For a second-order reaction, the rate of reaction is directly proportional to the square
of the concentration of one of the reactants. The differential rate law is given by the
following equation:

r = k[ A]2 (8.3)

The rate constant, k, has units of L/mole · s.

170 Chemical Engineering Primer with Computer Applications

The behavior of these three described rates is illustrated as follows:

1. For a zero-order reaction, the rate of reaction is constant as the reaction

progresses.
2. For a first-order reaction, the rate of reaction is directly proportional to the
concentration. As the reactant is consumed during the reaction, the concen-
tration drops and so does the rate of reaction.
3. For a second-order reaction, the rate of reaction increases with the
square of the concentration, producing an upward curving line in the
rate–concentration plot. For this type of reaction, the rate of reaction
decreases rapidly (faster than linearly) as the concentration of the reac-
tant decreases.

8.1.3.1.4 Integrated Rate Laws

As was demonstrated, the differential rate law describes how the rate of reaction
varies with the concentrations of various species, usually reactants, in the system.
The rate of reaction is proportional to the rates of change in concentrations of the
reactants and products, that is, the rate is proportional to a derivative of a concentra-
tion. This is explained as follows:
For the reaction

A®B

The rate of reaction, r, is simply described by

d[ A]
r=- (8.4)
dt

Assuming that this reaction is a first-order, as given by the following equation:

r = k[ A], (8.2)

one can write the rate equation as

d[ A]
r =- = k[ A] (8.5)
dt

This equation is a differential equation that relates the rate of change in a concentra-
tion to the concentration. By multiplying both sides of Equation 8.5 by dt/[A], one
obtains the following equation:

d[ A]
= - k dt (8.6)
[ A]
Reaction Kinetics, Chemical Reactors, and Thermodynamics 171

Integration of this equation between the time limits, t = o and t = t, gives the cor-
responding integrated rate law (Equation 8.7), which relates the concentration to
time:

[ A] = [ A]0 e - kt (8.7)

where at t = 0, the concentration of A is [A]0.

For each integrated rate law, there is a characteristic plot that can be cre-
ated that will produce a straight line. These characteristic plots are presented
in the following table; species A is a reactant in the chemical reaction (Dixon,
2002).

Slope of
Reaction Differential Characteristic Kinetic Units of Rate
Order Rate Law Integrated Rate Law Kinetic Plot Plot Constant

d éA ù
Zero - ë û =k [A] = [A]0 − kt [A] vs. t −k mole/L · s
dt
d éA ù
First - ë û = k éë A ùû [A] = [A]0 e−kt ln [A] vs. t −k s−1
dt
d éA ù éë A ùû 0
- ë û = k éë A ùû
2
Second éë A ùû = 1/[A] vs. t k L/mole · s
dt 1 + kt éë A ùû 0

The series of three graphs shown later illustrates the use of the characteristic kinetic
plots. The graph on the left shows [A] versus t plots for a zero-order (red line), first-
order (green line), and second-order (blue line) reaction. The graph in the middle
shows ln [A] versus t plots for each reaction order, and the graph on the right shows
1/[A] versus t plots for each reaction order.
172 Chemical Engineering Primer with Computer Applications

×10–3 100.00 –2.00

Concentration vs. time ln[concentration] vs. time

ln[concentration L/mole]
Concentration (mole/L)

Red
–4.00

50.00

Green

–6.00

0.00
0.00 5.00 10.00 0.00 5.00 10.00
Time (s) Time (s)

1000.00
1/concentration vs. time
1/concentration (L/mole)

500.00

Blue

0.00
0.00 5.00 10.00
x

8.2 PART II: TYPES AND DESIGN OF CHEMICAL REACTORS

8.2.1 introduction
Chemical reactors are generally classified into three main models:

1. Batch reactor model (batch)

2. Continuous stirred-tank reactor model (CSTR)
3. Plug flow reactor model (PFR)
Reaction Kinetics, Chemical Reactors, and Thermodynamics 173

On the other hand, there are two main basic vessel types (in accordance to their
shapes):

1. A tank reactor
2. A pipe or tubular reactor (laminar flow reactor)

Both types can be used as continuous reactors or batch reactors, and either may
accommodate one or more solids (reagents, catalyst, or inert materials), but the
reagents and products are typically fluids.
A chemical reactor, typically a tubular reactor, could be a packed bed. The pack-
ing inside the bed may have a catalyst to catalyze the chemical reaction. A chemical
reactor may also be a fluidized bed.
Furthermore, catalytic reactors require separate treatment, whether they are
batch, CST, or PF reactors, as the many assumptions of the simpler models are not
valid.

8.2.2 tyPes oF laBoratory and industrial catalytic reactors

Laboratory catalytic reactors include many types: pulse, batch, tubular (differential
and integral), CSTR, recycle, and transport. Figure 8.1 is an illustration of this group.
The details of CSTR are given in Figure 8.2.
Industrial catalytic reactors, on the other hand, cover different types such as fixed
bed, trickle bed, moving bed, fluidized bed, slurry, and monolith. This set of reactors
is schematically shown in Figure 8.3. The details of a fixed-bed reactor are shown
in Figure 8.4.

C0 C ΔC 0
(b)

(a) C0 C ΔC large

(d)

C0 C ΔC large C
+cat ΔC large
(c)

C0 C ΔC large
C0
+ cat
(e) (f)

FIGURE 8.1 Types of laboratory catalytic reactors: (a) pulse, (b) differential, (c) integral,
(d) CSTR, (e) recycle, and (f) transport.
174 Chemical Engineering Primer with Computer Applications

Motor
Feed

Cooling jacket

Baffle

Agitator

Mixed product

FIGURE 8.2 CSTR.

8.2.3 catalytic reactors

In a catalytic reactor, the rate of a catalytic reaction is proportional to

1. The effective amount of catalyst

2. The concentration of the reactants

With a solid phase catalyst and fluid phase reagents, this is proportional to the exposed
area, efficiency of diffusion of reagents in and products out, and efficacy of mixing.
The behavior of the catalyst is also a consideration. Particularly in high-temper-
ature petrochemical processes, catalysts are deactivated by sintering, coking, and
similar processes.
A common example of a catalytic reactor is the catalytic converter following an
engine. However, most petrochemical reactors are catalytic and are responsible for
most of industrial chemical production in the world, with extremely high-volume
examples such as sulfuric acid, ammonia, and reformate/benzene, toluene, ethylben-
zene, and xylene (BTEX).
A catalyst performance depends directly on the following four factors:

1. Activity
2. Selectivity
3. Life and stability
4. Economics and process costs
Reaction Kinetics, Chemical Reactors, and Thermodynamics 175

C0 C0
(a) (b)

C Liquid + catalyst

C0 C
C0 Liquid + catalyst
(c) (d)

C0 Liquid Catalyst C

C + Liquid C0 Catalyst
(e) (f )

C + catalyst
C

Catalyst

C0 + catalyst C0 + catalyst
(g) (h)

FIGURE 8.3 Heterogeneous catalysis reactor types: (a) fixed bed, (b) batch fluid bed,
(c) slurry, (d) catalytic gauze, (e) trickle bed, (f) moving bed, (g) continuous fluid bed, and
(h) transport line.

8.2.4 design oF cHemical reactors

Reactors are designed based on features like

1. Mode of operation, batch versus continuous

2. Types of phases present, homogeneous versus heterogeneous
3. Geometry of reactors, vessel versus tube
176 Chemical Engineering Primer with Computer Applications

Products and
unreacted materials
to separation

Catalyst on
support

Diffuser

Reactants

FIGURE 8.4 Fixed-bed reactor (e.g., this is used in the manufacture of ammonia).

Key process variables in chemical reaction engineering include

• Residence time (θ)

• Volume (V)
• Temperature (T)
• Pressure (P)
• Concentrations of chemical reactants (CA…)

8.2.4.1 Basic Design Equations

The parameter that has been commonly used as a measure of the reactor capacity is either

• The mean residence time θm

• The space time φ

Definition of θm: It is the average of time periods during which reaction mixtures
stay in the reactor and is given by the equation
dN A
qm =
ò V(-r ) ,
A
between the limits N A 0 and N Af (8.8)

where
NA is the number of moles of reactant A
V is the reactor volume
–rA is the rate of disappearance of A
Reaction Kinetics, Chemical Reactors, and Thermodynamics 177

In terms of the fractional conversion, xA, Equation 8.8 becomes

dx A
qm = N A 0
ò V(-r ) ,
A
between the limits 0 and x Af (8.9)

Under steady-flow conditions with constant fluid density, θm for a continuous flow
reactor may be calculated by using

V (8.10)
qm =
q

where q is the volumetric flow rate of the reaction mixture.

Definition of ϕ, the space time: It is defined as the time elapsed in processing one
reactor volume of feed at specified conditions. For example, if a value of ϕ is 1.5 h, it
implies that 1.5 h would be required to process a one rector volume of feed at known
conditions. It is given by the equation

V V V 1
f= = = = (8.11)
(F /) (FA 0 /CA 0 ) q 0 S

Sizing of a reactor may be illustrated by a general example for a PF reactor as illus-

trated in the following steps:

First: The space time can be estimated from

laboratory data through the expression:

φ = CA0 dxA/(–rA)

Second: The mathematical

expression for is given

= V/(F/ℓ) =
V/(FA0/CA0) = V/q0 = 1/S

Third:

Knowing the value of φ

from step (1),

find V = [FA0/CA0]
178 Chemical Engineering Primer with Computer Applications

where
F and FA0 are the flow rates in moles per unit time of the total feed and of reactant
A in the feed, respectively
 is the molar density in moles per unit volume of the feed
CA0 is the concentration of A in the feed
q0 is the volumetric flow rate of the feed at entering conditions
S is the space velocity

To summarize this, the required capacity of the reactor V is computed from the
specified feed rate and feed concentration of component A and with the knowledge
of space time, ϕ.

8.3 PART III: INTRODUCTION TO THERMODYNAMICS

8.3.1 Basic deFinitions and concePts
To start with, thermodynamics could be described as the study of energy conversion,
most typically through terms of heat and work.

8.3.1.1 The Concept of Equilibrium

The state of a system in which properties have definite, unchanged values as long as
external conditions are unchanged is called an equilibrium state (Figure 8.5).
A system in thermodynamic equilibrium satisfies

• Mechanical equilibrium (no unbalanced forces)

• Thermal equilibrium (no temperature differences)
• Chemical equilibrium

8.3.1.2 The Concept of a Process

If the state of a system changes, then it is said that it is undergoing a process. The
succession of states through which the system passes defines the path of the process.

8.3.1.3 Equations of State

It is an experimental fact that two properties are needed to define the state of any
pure substance in equilibrium or undergoing a steady-steady process.

Po
Mass A
Gas Gas
T1 T2 Insulation

Gas at
Copper partition
Mg + PoA = PA pressure, P
Over time, T1 T2

FIGURE 8.5 Illustration of mechanic and thermodynamic equilibrium.

Reaction Kinetics, Chemical Reactors, and Thermodynamics 179

Thus, for a simple compressible gas like air,

P = P(u, T), or u = u(P, T), or T = T(P, u) ,

where υ is the volume per unit mass, (1/), that is, if we know υ and T is the tem-
perature, we know P is the pressure, etc. Any of these is equivalent to the equation
f(P, u, T) = 0, which is known as an equation of state. The equation of state for an ideal
gas, which is a very good approximation to real gases at conditions that are typically
of interest for aerospace applications, is

Pu = RT,
where
u is the volume per mol of gas
R is the universal gas constant

8.3.2 tHermodynamic laws and entroPy

• Zeroth law: When two systems are both in thermal equilibrium with a third
system, then they must be in thermal equilibrium with each other, that is,
thermal equilibrium is transitive.
If Temp(A) = Temp(B) and Temp(B) = Temp(C), then Temp(A) = Temp(C).
• First law: The increase in internal energy of a closed system is equal to the dif-
ference of the heat supplied to the system and the work done by it: ΔU = Q–W.
Note that due to the ambiguity of what constitutes positive work, some
sources state that ΔU = Q + W, in which case work done on the system is
positive.
• Second law: The second law states that all work processes tend toward
greater entropy over time. Another way of saying this is that total entropy
of an isolated system can never decrease.
In other words, heat cannot spontaneously flow from a colder location to
a hotter location.
• Third law: As a system approaches absolute zero, the entropy of the system
approaches a minimum value.
The third law of thermodynamics is a statistical law of nature regarding
entropy and the impossibility of reaching absolute zero of temperature.

8.3.2.1 Entropy
The idea of entropy comes from a principle of thermodynamics dealing with energy.
It usually refers to the idea that everything in the universe eventually moves from
order to disorder and entropy is the measurement of that change. The following is a
list of definitions of entropy from a collection of textbooks:

• A measure of energy dispersal at a specific temperature

• A measure of disorder in the universe or of the availability of the energy in
a system to do work
• A measure of a system’s thermal energy per unit temperature that is unavail-
able for doing useful work
180 Chemical Engineering Primer with Computer Applications

We see evidence that the universe tends toward highest entropy many places in our
lives. A campfire is an example of entropy. The solid wood burns and becomes ash,
smoke, and gases, all of which are more disordered than the solid fuel. For isolated
systems, entropy never decreases. This fact has several important consequences in
science: it prohibits perpetual motion machines, it implies that the arrow of entropy
has the same direction as the arrow of time, and so on. Increases in entropy cor-
responds to irreversible changes in a system, because some energy is expended as
waste heat, limiting the amount of work a system can do.

8.3.3 role oF ∆g in cHemical reactions

For the general chemical reaction

r1
¾¾
aA + bB ¬ ¾ ® cC
¾ r2

The forward rate of the reaction is

r1 = k1[A]a [B]b

The backward rate is

r2 = k 2 [C]c

Now, at equilibrium

r1 = r2

Therefore,

k1[A]a [B]b = k 2 [C]c

and we get

k1 [C]c [ Products]
= Kp = =
k2 [A]a [B]b [ Reactants]

Given the free energy of formation of the reaction, ∆G, we can write

DG = -RT ln K p

where Kp is the equilibrium constant for the reaction at the given conditions of T and
P, expressed as the concentrations of the participating species in terms of the partial
pressures.
Reaction Kinetics, Chemical Reactors, and Thermodynamics 181

ΔG at constant temperature is also given as a function of entropy change:

DG = DH - TDS

where ΔH and ΔS are the increase in total heat content and entropy in the reaction,
respectively.

END-OF-CHAPTER SOLVED EXAMPLES

Part (a): manual calculations

Example 8.1

Calculate the entropy of the surroundings for the following two reactions:

(a) C2H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g)

DH = -2045 kJ

(b) H2O(l) → H2O(g)

DH = +44 kJ

Solution
The change in entropy of the surroundings after a chemical reaction at constant
pressure and temperature can be expressed by the formula

DH
DSsurr = -
T
where
ΔSsurr is the change in entropy of the surroundings
−ΔH is the heat of reaction
T is the absolute temperature in Kelvin

Reaction (a)

DH
DSsurr = -
T
-2045 kJ
DSsurr = -
25 + 273

**Remember to convert °C to K**

2045 kJ
DSsurr =
298 K
DSsurr = 6.86 kJ/K or 6860 J/K

Note that the increase in the surrounding entropy since the reaction was
exothermic.
182 Chemical Engineering Primer with Computer Applications

Reaction (b)

DH
DSsurr = -
T

+44 kJ
DSsurr = -
298 K

DSsurr = -0.15 kJ/K or -150 J/K

This reaction needed energy from the surroundings to proceed and reduced the
entropy of the surroundings.
Conclusions: The change in entropy of the surroundings of reactions 1 and 2 was
6860 and −150 J/K, respectively.

Example 8.2

The following example illustrates on how to determine the thermodynamic feasi-

bility of a chemical reaction:

2 H2 (g) + O2 (g) ® 2H2O(l)

We can calculate ΔrG° for this reaction from the tables of free energies of forma-
tion. We find that ΔrG° for this reaction is very large and of negative value, which
means that the reaction is very feasible. We conclude, right away, that the equilib-
rium constant, K, for the reaction is very large:

DG = -RT lnK

However, we can mix hydrogen gas and oxygen gas together in a container, even
in their correct stoichiometric proportions, and they will stay there for centuries,
perhaps even forever, without reacting. The problem is not that the reactants do
not want to form the products, they do, but they cannot find a pathway to get from
reactants to products. In other words, thermodynamics is not the only main focus
in chemistry. Not only do we have to know whether a reaction is thermodynami-
cally favored, we also have to know whether the reaction can or will proceed at a
finite rate. The study of the rate of reactions is called chemical kinetics.

Example 8.3

Methanol vapor can be converted into formaldehyde by the following reaction

scheme:

CH3OH + 0.5O2 ® HCHO + H2O

CH3OH ® HCHO + H2
Reaction Kinetics, Chemical Reactors, and Thermodynamics 183

The fresh feed to the process was 0.5 kmole/h of O2 and an excess methanol. All
of the O2 reacts in the reactor. Formaldehyde and water are removed from the
product stream first, after which H2 is removed from the recycled methanol. The
recycle flow rate of methanol was 1 kmole/h. The ratio of methanol reacting by
decomposition to that by oxidation was 3. Draw the flow diagram and then cal-
culate the per pass conversion of methanol in the reactor and the fresh feed rate
of methanol.
Calculations:
The flow diagram for the aforementioned process is given here:

Hydrogen
Recycle methanol
1 kmole/h Hydrogen
separator

Fresh feed HCHO and

Reactor water
Oxygen + separator
methanol
O2 = 0.5 kmole/h
HCHO + H2O

From the given statements, we apply the following:

• All of the O2 entering reacts in the reactor.

• The ratio of methanol reacting by decomposition to that by oxidation
was 3.

The numbers of moles taking part in the reactions are given as follows:

CH3OH+ 0.5 O2 ® HCHO+ H2O (8.3.1)

1 0 .5 1 1

CH3OH + ® HCHO+ H2 (8.3.2)

1 1 1

From reaction (8.3.1): In 1 h, 0.5 mole of O2 reacts with 1 mole of CH3OH.
Therefore, for complete conversion of oxygen, 0.5 moles/h of O2 needs
1 mole/h of CH3OH.
Obtaining the ratio of methanol conversion, we then find that the flow rate in
methanol decomposition is three times greater than that in methanol oxidation,
that is, 3 moles/h of CH3OH.
Therefore,
Total methanol entering the reactor = methanol reacted by oxidation + metha-
nol reacted by decomposition + recycled methanol = 1 + 3 + 1 = 5 kmoles/h
Conversion per pass = 100 × (total methanol reacted/total methanol entering
the reactor) = 100 × 4/5 = 80%
Fresh methanol rate = total methanol entering the reactor − recycled metha-
nol = 5 − 1 = 4 kmoles/h (Subbu, 2014)
184 Chemical Engineering Primer with Computer Applications

Part (B): using matlaB®

Example 8.4: Chemical Equilibrium Inside a Chemical Reactor

Methanol is formed by reacting carbon monoxide with hydrogen. (This might be

an onboard generation of hydrogen for the hydrogen economy.) With the reaction

CO + 2H2 Û CH3OH,

the condition at equilibrium is

PCH3OH y 1
Kp = = CH3OH
pCOpH22 yCOyH22 P2

When the carbon monoxide and hydrogen enter the reactor in a 1: 2 ratio, find the
equilibrium conversion when the pressure is 50 atm and Kp = 0.0016.

Feed Product
Equilibrium
1 mole CO reactor 1–x mole CO
2 moles H2 2–2x mole H2
x mole CH3OH

A conceptual model is formed as follows, where x is the fraction reacted from the
carbon monoxide at equilibrium.
Hence,

x (3 - 2x )
2
1
Kp = 0.0016 =
(1- x ) (1- x )
2
4 ´ 502

By solving this equation for x, the equilibrium conversion is found to be 0.50.

Solution could be obtained using Matlab,

Example 8.5

Methane is used to produce acetylene as the main product by the following ther-
mal reaction:

2CH4 (gas) + Q ® C2H2 (g) + H2 (g)

As an undesired side reaction, acetylene decomposes to give

C2H2 ® 2C(s) + H2 (g)

Reaction Kinetics, Chemical Reactors, and Thermodynamics 185

Given

• Methane is fed to the reactor at 1500°C, at a rate of 10.0 moles/s

• Heat is transferred to the reacting system at the rate of 975 kW
• The product temperature is 1500°C
• The % fractional conversion of methane is 60
• The enthalpy balance Q = DH = éê nH
ë åi i
ù
åé
úû products êë nH
ù
i ú
ûreactants
( )
• Hi = DH0f + Cpi (1500 - 25)
I

Calculate the product component flow rates and the yield of moles of C2H2/mole
of CH4. Also, calculate the yield of H2 per mole of H2 introduced to the reactor in
the form of CH4.

975 kW N1 mole CH4

N2 mole C2H2

10 mole CH4 (g)/s at 1500°C N3 mole C

Methane reactor

N4 mole H2

(Products/s)

Solution
The conversion rate of methane is 60%; hence, N1 = 10(1 − 0.6) = 4 moles CH4
(unreacted).
Carbon balance, in = out

10(1) = 4(1) + 2(N2 ) + N3

or

2N2 + N3 = 6 (8.5.1)

Hydrogen balance, in = out

10(4) = 4(4) + 2N2 + 2N4

or

2N2 + 2N4 = 24 (8.5.2)

Note that the moles of hydrogen in this balance are meant to be atoms of hydrogen.
Now, we have two equations and three unknowns (N2, N3, N4). We use the
enthalpy balance next to come up with the third relationship, in order to have
three equations in three unknowns.
186 Chemical Engineering Primer with Computer Applications

Q = DH = éê
ë ånH ùûú
i i
products
- éê
ë ånHùûú
i
reactants

975 = [4H1 + N2H2 + N3H3 + N4H4 ] - 10H1

Rearranging and substituting for the enthalpies, Hs with the corresponding values,
we obtain

303.45 N2 + 32.45 N3 + 45.72 N4 = 1225.08 (8.5.3)

Now, we can enter these three equations, 8.5.1 through 8.5.3, into the MATLAB
matrix form: A = xb. Solving for the value of

x = 2.4983; that is N2 , mole of C2H2 /s

= 1.0035; that is N3 , mole of C/s

= 9.5017; that is N4 , mole of H2 /s

Yield of acetylene = 2.4983/6 = 0.417 mole/mole of methane

Yield of hydrogen = 9.5017 / éë10 moles methane ´ 4 (hydrogen atoms per mole ) ùû
= 0.2375 mole /mole of methane

REFERENCES
Dixon, J., Espenson, J. H., Kinetics and mechanism of oxygen atom abstraction from a
dioxo-rhenium(VII) complex, Inorganic Chemistry 41: 4727, 2002.
Myers, R. The Basics of Chemistry, London, U.K.: Greenwood Publishing Group, 1951.
Subbu, M. Chemical Engineering Learning Resources, 2014. http://www.msubbu.in.
 9 Chemical Plant Design
and Process Economics

Safety and
Environmental
Health loss
problems
prevention

Plant General factors to be Plant

location considered layout

Technical aspects Plants dealing

Cost with chemical
estimation changes
Plant design Two main
Economics and economics types of
Profitability plants:
analysis
Design aspects Plants dealing
with physical
changes

Process design:
Design procedure: A–Z chart
1. A written description of
Feasibility study
the process
Process design 2. Make a qualitative BD
Economic evaluation
3. Perform MB and EB
Plant erection
Startup
Production

The successful convergence of theory and practice has a great impact on developing
courses in plant design. This chapter will highlight the different aspects involved in
the design of chemical plants. Since the topic is too involved, we attempt to provide
a balanced presentation to the strategy of process synthesis in plant design con-
sistent with industrial practice and within the economic frame of feasible projects.
The dollar sign must always be kept in mind when carrying out the design of a
chemical plant.
This chapter covers the basic fundamentals in plant design that the reader should
acquire, from the inception of an idea all the way to the construction of a plant.
Process design is a cornerstone in this presentation. General design considerations,

187
188 Chemical Engineering Primer with Computer Applications

complementary to the design of a plant, are discussed. These include safety,

health  hazards, and design aspects related to the plant location and plant layout.
The economic aspects involved in building a chemical plant, from cost estimation to
profitability studies, are presented. Illustrations of the use of computer-aided design
(CAD) to study the performance of process units in chemical plants and their inte-
gration into a complete plant are presented. Solved examples and sample problems
are used extensively in this chapter to illustrate the applications of principles to
practical situations.

9.1 INTRODUCTION
A chemical plant is one that belongs to the chemical industry. Most processes in
the chemical industry involve a chemical change, which could imply two distinctive
groups of industry:

1. One The first group of industry involves a chemical change, for example,
in the case of chemical reaction of nitrogen with hydrogen that produces
ammonia.
2. The second group of industry involves physicochemical change, involved in
the separation of a given feed to components or fractions, for example, the
distillation of hydrocarbons and water desalination. These industries are
normally recognized as physical separation operations that utilize strictly
unit operations.
Purely mechanical changes or separations are not considered part of the
chemical processing.

Plant design for processes of the first group utilizes, in its initial stage, the basic
chemical stoichiometric equations describing the chemical reactions, in order to
do material balance (MB) and heat balance (HB) calculations. However, for indus-
tries of the second group, calculations are usually based on setting up the total
MB and component MB, for example, the solution of binary-distillation problems
involved in the setting up of two equations in two unknowns, as was presented in
Chapter 6.

9.2 PLANT DESIGN IS THE HEART OF CHEMICAL ENGINEERING

Modern chemical engineers are concerned with processes that convert raw materials
or chemicals into more useful or valuable forms. They are also concerned with the
pioneering valuable materials and related techniques—which are often essential to
related fields such as nanotechnology, fuel cells, and bioengineering.
Students study many basic courses in chemical engineering that include chemical
reaction engineering, heat transfer, and thermodynamics. However, when it comes to
plant design, simulated by a heart as shown in Figure 9.1, all of these courses along
with other information represent the input and the output design, which is a profit-
able working entity.
Chemical Plant Design and Process Economics 189

Input

Heat transfer
Fluid mechanics
Diffusional (mass
transfer)
Kinetics and reactor
design
Instrumentation
and procees control
Output
Thermodynamics PD
A profitable
working plant
Fundamentals or process
of
economics

Design considerations:-
1. Plant location
2. Plant layout
3. Others

FIGURE 9.1 Plant design is the heart of chemical engineering.

In a plant design course, students are basically well prepared to launch a design
project, once they cover the following additional topics: economics, materials selec-
tion, computer-aided design (CAD), and optimization technique, and others. Their
personal information has an impact in handling a design project as well.

9.3 HOW TO HANDLE A DESIGN PROJECT?

9.3.1 ProPosed Procedure
The design of a chemical plant would normally go through the following steps:

• Derive an idea (e.g., to produce a product).

• Find out if it is feasible to build a plant (technical and economic feasibility
study).
• Carry out a process design that involves three basic stages:
• Draw a qualitative block diagram based on a written description for the
selected process.
• Carry out basic calculations using MB and EB to come up with a quan-
titative block diagram. MB is the basis of process design, as shown in
Figure 9.2.
• Determine the size and capacity of equipment (equipment sizing).
• Do cost estimation for the capital investment of the plant.
• Carry out profitability analysis for the project.
190 Chemical Engineering Primer with Computer Applications

Material
balance

Over the complete Over individual

process process units

To determine the quantities of raw To set the process stream flow

materials required and production rate and composition

FIGURE 9.2 The role of material balance in process design.

When it comes to computer applications, spreadsheet software has become an indis-

pensable tool in plant design because of the availability of personal computers, ease
of use, and adaptability to many types of problems. On the other hand, many pro-
grams are available for the design of individual units of chemical process units. The
Computer Aids for Chemical Engineering Education Corporation makes available
several programs mainly for educational use.

9.3.2 a–Z cHart For Plant design

In order to make the picture clearer, all steps to be carried out in a design project
are put together in the form of what is called A–Z chart, shown in Figure 9.3. It is

No

Inception of Library and Process Prelim

Start Evaluation
an idea market res. research eng. study

No
Economic Complete
Procurement Development
Detailed eval. process
based on
eng design preconst design
quotations
cost est.

Erection and Startup and Commercial

installation test run production

FIGURE 9.3 The A–Z chart in plant design.

Chemical Plant Design and Process Economics 191

a collective and comprehensive flowchart that takes the student through the whole
plant to be: from feasibility study to commercial production via the intermediate
steps of process design followed by economic evaluation.
In general, the following three cases of design projects are common to handle:

1. New process development

2. New production capacity to meet growing sales
3. Modification and addition to existing plant

9.3.3 Flow sHeeting and tyPes oF Flow diagrams

Flow sheeting, as used in CAD, means performing on a specified flow sheet, the
calculations necessary to simulate the behavior of the process. These calculations
include mass and energy balances.
Process design normally starts with a process scheme or flow sheet. A flow dia-
gram is the road map of a given process. It is the key document in process design.
It is a diagrammatic model of the process, which describes the process steps in a
proper sequence using symbols to represent the various components (equipment,
lines, and control instrumentation) that make up the unit. During the plant start-up
and subsequent operation, the flow sheet forms a basis for comparison of operating
performance with design. It is also used by operating personnel for the preparation
of operating manual and operator training.

9.3.4 scale-uP Practice and saFety Factors

Stages in the development in plant design follow the route, right after laboratory-
scale experiments, all the way to full-size commercial production, passing by bench
scale and pilot plant tests. These stages are illustrated in Figure 9.4.
Safety factors play an important role when dealing with a design project. It is
defined as the amount of overdesign in order to account for changes in operat-
ing performance of equipment or a vessel. A handout summary is illustrated in
Figure 9.5.

9.4 OTHER ASPECTS IN PLANT DESIGN

Apart from the engineering principles considered in the plant design, there are other
important functions and items to be considered regarding safety, health, loss preven-
tion, plant location, plant layout, and others.

Full size
Lab Bench Pilot commercial
scale scales plant production

FIGURE 9.4 Stages in plant design.

192 Chemical Engineering Primer with Computer Applications

(i) Definition: It is the amount of overdesign to account for changes in operating performance
of an equipment.
(ii) Applications: 1. To safeguard against fouling in: (a) heat exchangers and (b) furnace pipes
2. For potential increase in capacity requirements
(iii) Calculations for Ht Ex:
1. To find out if a given Ht Ex is fouled or not?

Q = UoA ∆Tm, Uo = 1/RT

RT = Total resistance = Rfi + Rw + Rf0 + Rsi + Rso, define Rsi + Rso = Rst

Inside Metal Scale

film wall Outside Scale outside
film
inside

Steps:
Calculate Uo = Q/A ∆Tm
Find the values of Rfi, Rfo, and Rw
Calculate Rst, using Uo = 1/[Rfi + Rfo + Rw+ Rst]
Compare the value of Rst, calculated, with the value for clean
Ht Ex....If Rst is >> 0.001, then the tube are fouled.

2. Safety factor for overdesign

It is estimated to be about 15%. In other words, increase the calculated area, A, by 15%
as a factor of safety.

FIGURE 9.5 Safety factors in design.

A brief summary is given as follows:

• Health and safety hazards: One should consider the toxicity of materials
and frequency of exposure, fire, and explosion hazards.
• Loss prevention: HAZOP study.
• Environmental protection and control include air pollution, water pollution,
solid wastes, thermal effects, and noise effects.
• For plant location: Both primary and specific factors are to be considered.
• For plant layout: Optimum arrangement of equipment within a given area
is a strategic factor.
• For plant operation and control: The designer should be aware of
• Instrumentation
• Maintenance
• Utilities
• Structural design
• Storage
• Materials handling, pipes, and pumps
• Patents aspects
Chemical Plant Design and Process Economics 193

9.5 THE ROLE OF ECONOMICS IN PLANT DESIGN

9.5.1 introduction
In this chapter, economic fundamentals as being applied to the design of chemical
plants are presented. This will involve two main tasks, as explained next:
The steps underlying both categories of cost estimation and profitability analysis
are indicated in Figure 9.6.

9.5.2 estimation oF tHe Fixed caPital investment

and tHe total caPital investment

Obviously, the estimation of the fixed capital investment (FCI) would enable the
designer to answer the following questions:

• How much capital do we need for a project?

• What are the annual depreciation costs of the physical assets of a plant?
• How much is the annual maintenance and repair costs of the equipment?
• How much is the working capital (WC)?

(1) (2)

Cost Profitability
estimation analysis

T. capital T. product
investment cost (TPC)

Fixed Working* General

Manufacturing
expenses

Direct Indirect†

1. Land
2. Process equipment
3. Buildings
4. Storage facilities
5. Utilities
6. Auxiliaries: workshops, laboratories, others
Apply
Calculate economic
income indicators

FIGURE 9.6 Economic aspects in plant design. *Working capital is the money needed for raw
materials and cash at start up and is equal to 10%–20% of T.C.I. †Indirect fixed capital is spent
in engineering expenses, supervision for construction and construction tools and equipment.
194 Chemical Engineering Primer with Computer Applications

Lang factors are recommended in this regard. Once the costs of delivered equipment
are estimated, factors are applied as shown next:

Factor to Estimate
Classification of the Plant Function FCI TCI
Solid processing operation 3.9 4.6
Solid/fluid processing operation 4.1 4.9
Fluid processing operation 4.8 5.7

The six-tenth factor is another handy method to determine the cost of an equipment
of a given capacity (A), if the cost and the capacity of a similar one (B) are known:

Cost of A = Cost of B × [Capacity of A/Capacity of B]0.6

9.5.3 decision making use oF annuity

An annuity is a series of equal payment paid at the end of the year, “A,” $/year. The
amount of an annuity, at the end of n years, will be equal to all payments plus interest
that accumulate, where i is the interest rate.
The future worth of this sum of money = A{(1 + i)n − 1}/i = A(SFF), where the
term {(1 + i)n − 1}/i is known as the sinking-fund factor (SFF).
Now, we have two cases:

1. If “A” deposited annually in this sinking fund is the annual depreciation

cost of an equipment, Ad, then the future worth of this Ad would simply
accumulate to P; the present value of the equipment:

é i ù
P = A d (SFF ) and A d = P ê ú
ë (1 + i) - 1 û
n

2. If “A” deposited annually, on the other hand, is the amount of the annual
capital recovery of the equipment, A r, then the amount of money generated
by the sinking fund will be the future value for the cost of this equipment:
F = Ar(SFF)

To make it clearer, the Ad, defined as the annual depreciation cost, when deposited in the
sinking fund, will generate the P of the equipment. This is simply to recover the original
cost paid in the equipment. On the other hand, when Ar(>Ad), defined as the annual
capital recovery, is deposited in the sinking fund, then the amount generated will be F.
In this case, F will be equal to P + the interest on P, as if it is deposited in a bank
for n year or simply

F = P(1 + i)n

This discussion is presented in a concise form as shown in Figure 9.7.

Chemical Plant Design and Process Economics 195

P ($)’s need to be invested

Bank Industry
Fb = P(1+i)n (1+i)n – 1
Fp = A
i
Let:
Fb = Fp

(1+i)n i
Ar = P
(1+i)n – 1 Sinking fund F (future value)

i
Ad = P Sinking fund P (present worth)
(1+i)n – 1

FIGURE 9.7 Investments in bank (F b) versus industry (Fp).

9.5.4 ProFitaBility analysis using economic indicators

The basic aim of financial measures and profitability analysis is to provide some
yardsticks for the attractiveness of a venture or a project, where the expected benefits
(revenues) must exceed the total production costs.
The most common measures, methods, and economic indicators of economically
evaluating the return on capital investment are

1. Rate of return or return on investment (ROI)

2. Payment period (PP)
3. Discounted cash-flow rate of return (DCFR) and present value index (PVI)
4. Net present value (NPV)

9.5.4.1 The Annual Rate of Return

It is defined by the equation:

Annual profit
ROI = 100
Capital investment

For projects, where the cash flow extends over a number of years, the average rate of
return is calculated using an average value for the profit, by dividing the sum of the
annual profits by the useful lifetime:

é
åAnnual profits/n ùú
n

ê 1= y
ROI = ê ú 100
ê (capital investment) ú
ë û
196 Chemical Engineering Primer with Computer Applications

9.5.4.2 Payout Period, Payback Time, or Cash Recovery Period

Payout period is defined as the time required for the recovery of the depreciable
capital investment in the form of cash flow to the project. Cash flow would imply the
total income minus all costs except depreciation.
Mathematically, this is given by Equation 6.2, where the interest charge on capital
investment is neglected:

Depreciable capital investment

Payout period (years)(PP) =
Average annual cash flow

9.5.4.3 Discounted Cash Flow Rate of Return and Present Value Index
If we have an oil asset (oil well, surface treatment facilities, a refining unit, etc.) with
an initial capital investment “P,” generating annual cash flow over a lifetime n, then
the DCFR is defined as the rate of return or interest rate that can be applied to yearly
cash flow so that the sum of their present value equals P.
From the computational point of view, DCFR cannot be expressed by an equation
or formula, similar to the previous methods. A three-step procedure involving trial
and error is required to solve such problems, as illustrated in the solved example in
Example 9.3.

9.5.4.4 Net Present Value

The DCFR method is based on finding the interest rate that satisfied the conditions
implied by the method. Here, we provide a value for i that is an acceptable rate of
return on the investment and then calculate the discounted value (present value) of
the cash flow using this i. The net present value is then given by

NPV = (present value of cash flow discounted at a given i) - capital investment

END-OF-CHAPTER SOLVED EXAMPLES

Example 9.1

In a gas plant, a stream of natural gas is processed in order to recover the valu-
able hydrocarbons C2 and C3/C4 and to sell the bulk of methane (C1) as a fuel gas,
sales gas.

Sales gas (C1) …….. S

Feed: n.g.
Gas plant C2………… E
F
C3/C4……. P
Chemical Plant Design and Process Economics 197

The feed rate is 2.5 × 106 g ⋅ mole/h. The feed gas composition is as follows:

Component Mole%
C1 83.0
C2 12.0
C3 4.0
n‐C4 1.0

Product specs are the following

• Sales gas contains negligible C3/C4.

• C2 product contains 1.0 mole% C1, 2.0 mole% C3, and no C4.
• C3/C4 product contains no C1, 2 mole% C2, and all of n‐C4.
• Calculate the flow rates for each of the product streams, assuming
that the sales gas is sold with 0.0 mole fraction of C2.
• Repeat for 0.01 and 0.05 mole fraction of C2.

Solution
Mole balance will give the following

For C1 0.83F = y1S + 0.01E + 0 (9.1.1)

For C2 0.12F = y 2S + 0.97E + 0.02P (9.1.2)

For C3 0.04F = 0 + 0.02E + y3P (9.1.3)

For C 4 0.01F = 0 + 0 + y 4P (9.1.4)

Given

y1 + y 2 = 1.0 (9.1.5)

0.02 + y3 + y 4 = 1.0 (9.1.6)

We have six equations and seven unknowns; F is given. Since the value of C2 in
the sales gas, y1, is specified to be 0.0, the solution is obtained readily as follows:
Answer

S = 2.07 ´ 106

E = 0.31´ 106

P = 0.12 ´ 106

Example 9.2

In the process design of a chemical plant, it is required to calculate the unknown

mass flow rates of each outlet stream for the given separation system. The inlet
198 Chemical Engineering Primer with Computer Applications

mass flow rate (kg/h) and the mass fractions of each species in the inlet (stream 1),
F, and each outlet are known.

F1 = ?
Solution
A = 4%
If we define the unknowns as
B = 93%
x1 = F1, x2 = F2, x3 = F3
and set up the mass balances for C = 3%

F = 10 F2 = ?
1. The total mass flow rate
x1 + x2 + x3 = 10 A = 20% A = 54%
B = 60% B = 24%
2. The mass balance on species 1
C = 20% C = 22%
0.04x1 + 0.54x2 + 0.26x3 = 0.2*10
3. The mass balance on species 2
0.93x1 + 0.24x2 = 0.6*10
These three equations can be written in matrix form

1 1 1 x1 10
F3 = ?
0.04 0.54 0.26 x2 = 2
A = 26%
0.93 0.24 0 x3 6 B = 0%
C = 74%
To find the values of unknown flowrates write the code:

A = [1,1,1;.04,.54,.26;.93,.240
, ]; B = [10;.2*10;.6*10];

X = A \ B; F1 = X(1), F2 = X(2), F3 = X(3)

The results will be

F1 = 5.8238

F2 = 2.4330

F3 = 1.743

Example 9.3

The capital cost of a heat exchanger, P, is $10,000 with a lifetime of 10 years. If the
money can be invested at 6% (annual interest rate), calculate

(a) The annual depreciation costs

(b) The annual capital recovery, if P is deposited in a bank at 6%
(c) Compare between the two values

Solution

(a) Calculation of Ad = 10,000[(0.06)/{(1.06)10 − 1}] = $759.0

(b) Calculation of Ar = P{[i(1 + i)n]/[(1 + i)n]} = 10,000(0.1359) = $1,359.0
Chemical Plant Design and Process Economics 199

(c) The difference between the two values is = 1359–759 = $600; the
interest on the capital, if invested in a sinking fund, gives 600(13.18) =
$7911

The Ar, on the other hand, if invested in sinking fund, should give

1359(13.18) = $17, 911,

which should break even with P, if deposited in a bank:

10, 000(1+ 0.06)10 = $17, 911

Example 9.4

Assume an oil company is offered a lease of oil wells that would require a total
capital investment of $110,000 for equipment used for production. This capital
includes $10,000 working money, $90,000 depreciable investment, and $10,000
salvage value for a lifetime of 5 years.
Cash flow to project (after taxes) gained by selling the oil is as given next.
Based on calculating the DCFR, a decision has to be made: should this project be
accepted?

Year Cash Flow ($103)

0 −110
1 30
2 31
3 36
4 40
5 43

Solution
Our target is to set the following equity: by the end of 5 years, the future worth of
the cash flow recovered from oil sales should break even with the future worth of
the capital investment, had it been deposited for compound interest in a bank at
an interest rate i. This amounts to say that

Fo = Fb

where
Fb = 110,000(1 + i)5 for banking
Fo = Si5=1Fi for oil investment that represents the cash flow to the project, com-
pounded on the basis of end-of-year income; hence

Fo = 30, 000(1+ i)4 + 31, 000(1+ i)3 + 36, 000(1+ i)2

+ 40, 000(1+ i) + 43, 000 + 20, 000
200 Chemical Engineering Primer with Computer Applications

Notice that the $20,000 represents the sum of WC and salvage value; both are
released by the end of the fifth year. Setting up FB = Fo, we have one equation
involving i as the only unknown, which could be calculated by trial and error.
The value of i is found to be 0.207, that is, the DCFR = 20.7%.

Example 9.5

Calculate the NPV of the cash flow for the oil lease described in the example
earlier, if the money is worth 15%.
Solution
At i = 0.15, the annual cash flow is discounted. The present value of the sum of
the cash flows = $127,000.

NPV = 127, 000 - 110, 000

= $17, 000

That is, the oil lease can generate $17,000 (evaluated at today’s dollar value) more
than and above the totally recovered capital investment. Solution is illustrated in
Table 9.1:

TABLE 9.1
DCFR: Results for Solved Example 9.4
i = 5% i = 20% i = 25% i = 20.7%
Year Cash Present Present Present Present
(y) Flow dy Value ($) dy Value ($) dy Value ($) dy Value ($)
0 110,000
1 30,000 0.8696 26,088 0.8333 24,999 0.8000 24,000 0.8290 24,870
2 31,000 0.7561 23,439 0.6944 21,526 0.6400 19,840 0.6870 21,297
3 36,000 0.6575 23,670 0.5787 20,833 0.5120 18,432 0.5700 20,520
4 40,000 0.5718 22,872 0.4823 19,292 0.4096 16,384 0.4720 18,880
5 43,000 0.4971 21,375 0.4019 17,282 0.3277 14,091 0.3910 16,813
20,000
Total 117,444 103,932 92,747 102,380
P.V.I 1.07 0.94 0.84 0.93
N.P.V $7,444.40 −$6,067.70 −$17,252.90 −$7,620.00
 10 Case Studies

10.1 INTRODUCTION
This chapter is best introduced by recalling the definition that chemical engineering
is the field that applies the core scientific disciplines of chemistry, physics, biology,
and mathematics to transform raw materials or chemicals into more useful or valu-
able forms, invariably in processes that involve chemical change.
Case Studies in Chemical Engineering is one of a set of resources published
by the chemical company ECI between 1971 and 1982. The booklets were the
result of a series of workshops at which contributors from industry and schools
collaborated.
The booklet is perhaps only of historical interest, but it does show how the
principles of chemical engineering were applied to improve the existing processes
and devise new ones in the days before the principles of green chemistry had been
enumerated.
CACHE (Computer Aids for Chemical Engineering; CACHE Corporation, 2016)
Process Design Case Studies represents an outstanding resource of many case
studies. These are covered in 11 different volumes that span “Separation System for
Recovery of Ethylene and Light Products from Naphtha Pyrolysis Gas Steam” in
Volume 1, all the way to “Conceptual Design of an Aromatics Plant from Shale Gas”
in Volume 2.
In Chapter 10, we attempt to introduce a number of case studies that touch on
practical technical problems, some of which the author has personally experienced
in his research work, both in academic institutions and in industry. Many of the
principles and fundamentals presented in the preceding chapters of our book are
introduced and illustrated as given in these case studies. Case studies 5 and 6
are taken from the open literature. The list of case studies presented includes the
following:

• Case Study 1: Alternatives to Storage of Ammonia

• Case Study 2: Flash Dewatering of Raw Sewage Effluents
• Case Study 3: Magnesium Extraction from Seawater
• Case Study 4: Chemical Desalting of Brines: An Avenue toward Global
Sustainability
• Case Study 5: Reactive Distillation
• Case Study 6: Applications of Differential Equations

201
202 Chemical Engineering Primer with Computer Applications

10.2 CASE STUDY 1: ALTERNATIVES TO STORAGE OF AMMONIA

10.2.1 introduction
In a process proposed for desert development by Abdel-Aal, ammonia is to be synthe-
sized by using solar hydrogen produced by water electrolysis, as shown in Figure 10.1.
For this process, storage tank facilities are needed to store ammonia. It is esti-
mated to store the amount of 60,000 tons of ammonia yearly.

10.2.2 tHe ProBlem

Outline the possible alternatives to store the ammonia; propose the one you rec-
ommend most. Carry out the calculations you deem necessary to support your
recommendations.

10.2.3 aPProacH
The possible alternatives are

• Liquid at ambient temperature under its vapor pressure

• Liquid at atmospheric pressure refrigerated to its boiling point
• A solution in some solvent, say water, which lowers the vapor pressure and
allows less elaborate containment

Step 1: Since ammonia is a vapor under normal conditions, one might store it
in large gasholders. This idea is ruled out because of the excessive volume
of ammonia at standard T and P, as shown next.

V = (60, 000 tons)(2000 lb/ton)(1/17)1b-mole/lb)(370) SCF/lb-mole = 3 ´ 103 ft 3

Comment: A tank 100 ft high and a mile in diameter is not sufficient!

Reject brines
Soda ash and
CO2 magnesium
NH3 chloride products
Chemical reactions to
convert saline water Ammonium
NH3
into valuable products chloride and partially
synthesis
desalted water
H2 Raw mat. Ammonia-based
Solar energy
Water fertilizers
electrolysis Source
of energy

Desert development

FIGURE 10.1 From solar hydrogen to desert development using ammonia.

Case Studies 203

Step 2: Let us calculate the vapor pressure of liquid ammonia at low temperatures.

Vapor Pressure (atm) Temperature (°F)

1 −28
5 41
10 78

Let us assume that ammonia can be stored as a liquid at its normal boiling
point. Then, we have to take into consideration the heat losses from ammo-
nia tank to the atmospheric conditions.
Step 3: The primary resistance to heat transfer would be offered by the tank–
air interface, with h equal to about 10 Btu/h · ft2 · °F and k, of an insulation,
is assumed to be equal to 0.15 Btu/h · ft · °F.
The surface area of the tank exposed to the atmosphere is

A = (5p / 4)(4V/p)2 / 3

where

V = 60, 000 ´ 2,000 ´ 1/50 (ft 3 /lb) = 2.4 ´ 106 ft 3

Therefore,
A = 8.5 × 102 ft2
The heat transfer rate is estimated as a function of the insulation thickness
X (inches):

Q = UA DT = [1/10 + X/ 0.15]-1 (8.5 ´ 106 ) Btu/h

Calculations are done as follows:

X, Insulation Thickness (in.) Q, Transferred (Btu/lb)

0.0 (no insulation) 8.5 × 107
6.0 2.1 × 105
12.0 1.1 × 105

10.2.4 conclusions
It is observed that the heat transfer Q to the ammonia storage tank would lead to
excessive loss of ammonia. Even with a foot of insulation, about 105 Btu/h will be
transferred into the tank. This will result in the boiling of about 200 lb of ammonia
per h (1 Btu vaporizes 590 lb ammonia).
It is therefore suggested to use 6 in. insulation that reduces the heat loss to

Q = 2.1 ´ 105 Btu/h.

204 Chemical Engineering Primer with Computer Applications

Safety precautions have to be applied and start-up purge plan has to be considered
to eliminate hazards of explosion involved during filling. In addition, the storage
capacity of 60,000 tons could be divided into two units: one for loading and the other
for unloading.

10.2.5 discussions
1. Consider other possibility to store ammonia in a solid compound, from
which ammonia is released as demanded; is it a feasible proposal?
Could large underground cavern be considered as another option?
2. An optimization model could be carried out to calculate the optimum insu-
lation thickness for the storage tank. This could lead to a substantial savings
when choosing a small insulation thickness.

10.3 CASE STUDY 2: FLASH DEWATERING

OF RAW SEWAGE EFFLUENTS
10.3.1 introduction
Sewage treatment is the process of removing contaminants from wastewater, primar-
ily from household sewage such as toilet flush, bath tubs, and washing machines.
As shown in Figure 10.2, the treatment process normally involves many steps. Most
important is the primary treatment, where the bulk of sludge is separated from the
water.

10.3.2 tHe ProBlem

The Janicki Bioenergy Omni Processor (2) started as a proof-of-concept project,
funded by the Bill and Melinda Gates Foundation in 2013. It was originally designed
to take in sewer sludge and primarily output electrical power. During the develop-
ment, it became clear that making clean drinking water made the processor more
economically viable, and a water treatment system was added.
It is known that sewage effluents contain more than 90% water. Basically, the
dewatering process is simply a kind of evaporation.
As a chemical engineer, make use of the fundamentals you learned in unit opera-
tions to propose a scheme to carry out this treatment.

10.3.3 ProPosed scHeme

The scheme proposed is illustrated in Figure 10.3 and a schematic outline is given
in Figure 10.4 as well. It utilizes the concept of multistage flash evaporation (MSFE)
commonly used in the desalination of seawater. Before this evaporation step is car-
ried out, the water content of the sewage effluents could be reduced to half its initial
volume by the application of the primary treatment as illustrated in Figure 10.2.
Water collected at this stage could be utilized for irrigation.
 Case Studies

The sewage treatment process

6
1 2 Sludge
Taking the treatment 7
wastewater Screening 5
Back to
away 4 Final the river
3
Secondary treatment
Primary
treatment treatment

FIGURE 10.2 Sewage treatment process. (After Thames Water, Facts and Figures, http://www.thameswater.co.uk/about-us/4625.htm, retrieved on
May 31, 2014.)
205
206 Chemical Engineering Primer with Computer Applications

Air extraction (vacu)

A
A Sewer sludge
Heating
steam

Water

Dewatered sludge

Heat input
Power Incineration
generation Resd
Exhaust steam

Electricity

FIGURE 10.3 Proposed scheme for treating sewage sludge to produce water and electricity.

A
B
F H
C
G

D
E

FIGURE 10.4 Schematic of a once-through multistage flash evaporator. Notes: A, steam

in; B, sewage feed in; C, condensed water out; D, dewatered sludge out; E, condensate out;
F, heat exchanger; G, condensation collection of water; H, sewage steam water heater (boiler).
(Modified after Winter, T., Pannell, D.J., and McCann, L. The Economics of Desalination
and Its Potential Application in Australia, SEA Working Paper 01/02, Agricultural and
Resource Economics, Perth: University of Western Australia, 2001. http://www.general.uwa.
edu.au/u/dpannell/dpap0102.htm, retrieved on November 13, 2006.)

10.3.4 Process descriPtion

Sewage waste effluent, say the feed, is pumped into the heat exchanger (dryer)
located in the top of the flashing chamber (stage 1), as shown in Figure 10.3. This
way it gains heat from the uprising hot water vapor, which condenses as a prod-
uct. The feed keeps moving to the next stage, which is then subjected for fur-
ther heating inside the steam heater. As it enters stage 2, its temperature is above
the boiling point at the pressure maintained at this stage. Therefore, a fraction of
the water boils ( flashes) to steam, thereby reducing the temperature until equi-
librium is reached. The resulting steam is a little hotter than the feedwater in the
Case Studies 207

heat exchanger. The steam cools and condenses against the heat exchanger tubes,
thereby heating the feedwater as described earlier. By that time, the sewer sludge
has been subjected to boiling, a process that removes all liquid, to be captured as
water vapor upon flashing inside the chambers.
The water is collected through troughs located beneath the heat exchangers (A).
Further treatment and ultrarefining steps are carried out for the produced water,
making it suitable for drinking.
Dewatered sludge is directed to an incinerator, which produces high-pressure
steam that fuels a generator. The generator creates electricity that is used as a source
of power. There is even a little extra electricity left that can be transferred into the
power grid. Exhaust steam, on the other hand, is used for heating purpose and for
steam-jet ejector to create a vacuum.
Based on daily basis, the results of S200 Omni Processor are reported as follows:

1. Plant input
a. A quantity of 10–12 tons of dry fuel
b. It could be
i. Any kind of biomass from sewage sludge
ii. Animal by-products
iii. Agricultural by-products
iv. Garbage (glass- and metal-free)
The fuel does not have to be dry as such. It can contain an appre-
ciable amount of water: 12 tons of fuel can hold up to 70 tons of
water.
Arrangement can be made to have a feed input that contains a mix-
ture of
A. Sewage feed, having more than 90% water
B. Sludge or other solid material, having 30%–90% water
2. Plant output
Three items are produced:
a. The power output is 300 kW.
b. The water output has a total volume of 70,000 L (water produced will
be clear and sterile, but with residual odor; ultrapurification equipment
is required to make it odor-free).
c. About 10%–20% of the dry material input will come out as ash.

10.3.5 conclusions
The proposed scheme presented in our chapter consists of two stages. However,
the number of flashing units (chambers) could multiple. This number is a function
of the water content and the type of sludge. The advantage of applying vacuum in
the first unit is obvious to reduce the temperature in the next units causing flashing
of the entering feed. In addition, reduction of vacuum inside the chambers leads
to lower operating pressure, and hence lower operating temperatures as seen in
Figure 10.5.
208 Chemical Engineering Primer with Computer Applications

0.19 0.12 0.05

bar bar bar

FIGURE 10.5 A module for multistage flashing operation.

Additional economic advantages are obtained when solar energy is considered in

heating and boiling instead of steam.

10.3.6 discussions
1. Derive the flash evaporation equation that applies for a single component
using a heat balance to predict how much is vaporized from the feed to the
evaporator. In this case, it will be assumed that the feed contains the solid
material (A) suspended in a bulk of water, similar to seawater with soluble
sodium chloride.
2. Elaborate on the incineration process. What are the basic design parameters
to consider in building an incineration furnace?

10.4 CASE STUDY 3: MAGNESIUM EXTRACTION FROM SEAWATER

10.4.1 introduction
The availability of magnesium metal from seawater plays a significant role in mak-
ing such a strategic metal to compete with other used metals. It is only two-thirds as
dense as aluminum. It is easily machined, cast, forged, and welded. It is used exten-
sively in alloys, chiefly with aluminum and zinc and with manganese.
It is worth mentioning that magnesium is ranked as the eighth most abundant
element in the Earth’s crust. One cubic kilometer of seawater contains a minimum
of one million tons of magnesium, which makes the sea a storehouse of about
1.7 × 1024 tons. Magnesium (Mg) is found in seawater as ions of magnesium. It is
typically extracted from seawater on an industrial scale in a process known as the
Dow process by precipitating it as magnesium hydroxide and then converting it to
magnesium chloride using hydrochloric acid.
Case Studies 209

10.4.2 ProPosed metHod

In the proposed method, known as preferential salt separation (PSS), magnesium
chloride is directly obtained from seawater and is used as a feedstock to manufacture
magnesium. The whole scheme is illustrated as shown in Figure 10.6.
The extraction of magnesium chloride from seawater is done first, using solar
energy to vaporize a dynamic stream of preconcentrated seawater flowing along an
inclined preferential salt separator (PSS). Magnesium chloride salts soluble in sea-
water will separate as the very end product. Distilled water will be produced as a
by-product in this phase. It represents a typical feed of water for hydrogen production
by electrolysis.

Solar energy

Photovoltaic array

Sea water
Brine
Desalination Preferential salt separator

Fresh water Anhydrous magnesium chloride

Electrolysis cells
Water Magnesium
electrolysis Magnesium
removed by
chloride
Anode Chlorine gas
vacuum
Magnesium
metal

H2
Electrolyte

Magnesium

Hydrogen generation Hydrogen storage

(Mg/Fe galvanic cell) (Mg hydride)

FIGURE 10.6 Proposed scheme for magnesium production from seawater.

210 Chemical Engineering Primer with Computer Applications

10.4.3 Production oF magnesium metal From magnesium cHloride

Anhydrous magnesium chloride is electrolyzed next, using the energy generated by
solar power in order to produce magnesium metal. Once produced, magnesium rep-
resents a reliable source of stored energy that could be exported by air, sea, or other
means of transportation to remote locations for the production of hydrogen. Another
option is to use magnesium to store hydrogen in the form of magnesium hydride.
Recent advances in system integration enable a sustainable and stable power supply
from solar systems.

10.4.4 discussions
1. Draw a block diagram for the aforementioned process, indicating the type
of operation in each step: physical (unit operation) or chemical conversion
(unit process).
2. Identify the chemical reactions that take place.
3. Compare between the proposed method of extracting Mg chloride from
seawater (PSS) and the one in current practice by Dow Chemical Company.

10.5 CASE STUDY 4: CHEMICAL DESALTING OF BRINES

10.5.1 introduction
Innovations in chemistry have a great effect on separation and processing in chem-
ical industries. As a matter of fact, many important chemical revolutions center
about the discovery of new reaction paths, such as the one we are considering in
this paper.
Solvay process is taken into account, which is referred to as the ammonia–soda
process. It is the major industrial process for the production of soda ash (sodium
carbonate). The ammonia–soda process was developed into its modern form by
Ernest Solvay during the 1860s. The ingredients for this process are readily avail-
able and inexpensive: salt brine (from inland sources or from the sea) and limestone
(from mines). A similar approach was followed by Abdel-Aal [1,2], but with different
objectives. The target is to desalt high-saline water resources using ammonia and
carbon dioxide to produce partially desalted water along with soda ash and other
chemicals.
Along this line, it could be stated that while the soda ash is the main product
in the Solvay process, it is a by-product in the proposed chemical desalting pro-
cess. The main product is partially desalted water that contains ammonium chlo-
ride, which may be called fertile water, which will then be used for agricultural
purposes.

10.5.2 metHodology
In its general term, desalting refers to a water treatment process that removes salt
from saline water resources. It is simply represented as follows:
Case Studies 211

We admit saline water

Conventional
Source of energy desalting Brine
process

Fresh water

The proposed chemical desalting process, on the other hand, when compared to the
conventional desalting process, differs on the following grounds:

1. Two chemicals, CO2 and NH3, are used in lieu of energy.

2. The feed is saturated brine or natural salt rocks.
3. Two main products are obtained:
a. Partially–desalinated water that contains ammonium chloride (NH4Cl)
to produce fertile water
b. Sodium carbonate (Na2CO3), which is known as soda ash

The process is represented schematically by the following scheme:

NH3 CO2

Chemical
Brine (sat.) desalting Soda ash

Fertile water
(contains NH4Cl)

It could be safely stated that the chemical desalting process complements seawater
desalination.

10.5.3 main reactions

The basic reactions involved could be visualized to take place as follows:

• Primary reaction: The reaction between CO2 and NH3 is described as follows:

CO2 + NH 3 ® NH 2COOH ëécarbamic acid ùû (10.5.1)

NH 3 + NH 2COOH ® NH 4 + + NH 2COO- [carbamate] (10.5.2)

The net reaction is CO 2 + 2NH 3 ® NH 2COO - + NH 4 + (10.5.3)

212 Chemical Engineering Primer with Computer Applications

• Secondary reaction: In the bulk of the solution, the carbamate hydrolyzes

comparatively slowly to bicarbonate:

NH 2COO - + H 2O ® NH 3 + HOCOO - (10.5.4)

• Product formation reaction

Now, in the presence of NaCl, the following instantaneous reaction takes place:

NH 4 + HCO3- + NaCl ® NaHCO3 + NH 4Cl (10.5.5)

This leads to the precipitation of sodium bicarbonate leaving ammonium chloride in

a partially desalinated solution.

10.5.3.1 Process Synthesis with Modifications

Sea oceans are a virtually inexhaustible source of magnesium. About 1 lb of magne-
sium is recovered from each 100 gal of seawater. Adding ammonia to our system will
trigger the precipitation of magnesium as magnesium hydroxide Mg(OH)2, which is
separated as an intermediate product, as shown in Figure 10.7. This is a turning point
in our process synthesis that will lead to the formation of NH3 to be recycled as given
by the following equation:

2NH 4Cl + Mg(OH)2 ® Mg(Cl)2 + 2NH 3 + 2H 2O (10.5.6)

The separation of magnesium chloride as a product adds an economic value to the

process.

10.5.3.2 Consumption–Production Analysis

The process involves the following reactions:

Reaction 1: 4NH 3 + 4H 2O ® 4NH 4OH (use 4 moles of NH 3 )

Fresh water
Seawater
M S F pant

Brine (30%)

NH3 Mg(OH)2
Absorber Double MgCl2
NH4Cl decomposition

NH4OH
Separation
CO2 Formation of
chemical NH3
products regeneration
Soda ash
(Na2CO3)
NH3 recycle

FIGURE 10.7 Block diagram for the proposed process.

Case Studies 213

Reaction 2: 2NH 4OH + Mg(Cl)2 ® Mg(OH)2 + 2NH 4Cl

Reaction 3:
2NH 4OH + 2CO2 + 2NaCl ® 2NaHCO3 + 2NH 4Cl (use 2 moles of NH 4OH)

Reaction 4: 2NaHCO3 ® Na 2CO3 + CO2 + H 2O

The consumption–production analysis is figured out as indicated in Table 10.1:

For process synthesis, the mass flow rates of the raw materials in and the products
out could be readily calculated using any convenient basis for the flow rate input of
saline brine containing 25%–30% sodium chloride as a saturated solution.
It should be noted that the number of moles of H2O shown earlier are provided by
the saline water upon admitting the ammonia gas into it. For CO2 gas, it is recom-
mended to use 2 moles as given in Equation 10.5.3. Partially–desalted water W, and
is shown by * in Table 10.1, is obtained as a product, after separating the soda ash
and magnesium chloride. If reaction given by Equation 10.5.6 applies to generate
NH3 for recycling, MgCl2 is produced in this case.

10.5.3.3 Comparison between the Solvay Process

and the Proposed Process
This comparison is done along the following lines:

Parameters Solvay Proposed

RM Salt brine (rock salt) Salt brine/desalination brines
Limestone+ CO2*
Metallurgical coke NH3 (recycle)

NH 3 ( recycle )

NH 3 ( regeneration ) 2NH 4Cl + Ca(OH)2 ® 2NH 3 + CaCl 2 + 2H 2O

2NH 4Cl + Mg(OH)2 ® 2NH 3 + MgCl2 + 2H 2O

Products Soda Ash Soda Ash

MgCl2
Partially desalted water, W

10.5.3.3.1 Important Notes

• For Solvay process, metallurgical coke burns limestone, CaCO3, to give
CaO + CO2 quick lime; CaO is slacked by water: CaO + H2O → Ca(OH)2.
• For the proposed process, the source of CO2 is the combustion of fossil fuels
in power generation and water desalination plants.
 214

TABLE 10.1
Consumption–Production Analysis for the Chemical Desalting Process
Reactants Products
Reactions NH3 H2O CO2 MgCl2 NaCl NH4OH Mg(OH)2 NaHCO3 Na2CO3 NH4Cl CO2 W
No. 1 −4 −4 +4
No. 2 −1 −2 +1 +2
No. 3 −2 −2 −2 +2 +2
No. 4 −2 +2 +1
Net −4 −4 −1 −1 −2 0 +1 0 +2 +4 *
Chemical Engineering Primer with Computer Applications
Case Studies 215

10.5.4 conclusion
The proposed process offers a scheme that provides three products as compared to
one product only by the Solvay process. Magnesium chloride is an important product
for the manufacture of magnesium metal. As a matter of fact, one can claim that the
proposed process could compete with the well-known Dow process for the extrac-
tion of magnesium chloride from seawater.
The process synthesis suggested in this paper focuses on the use of ammonia
as a recycle reagent. Regeneration of ammonia is accomplished in the absence of
Ca(OH)2 used in the Solvay process as indicated in the earlier comparison.
The production of fertile water (partially–desalted water) containing NH4Cl
could be a feasible choice; NH4Cl could be sold as a solution to be used in fertilizers
for rice crops.

10.5.5 discussion and ProBlem Formulation

1. Check the values presented in Table 10.1 for the consumption–production
analysis for the chemical desalting process.
2. Do a material balance for the process to calculate the quantities of the feed
raw materials and the products obtained by processing a feed of 20 × 106
gallon per day (GPD) of seawater to be flashed, first in the MSF plant to
produce 15 × 106 GPD of brine, with a salt concentration of about 7%.
Waste–heat energy is used for salt concentration to raise the salt content
in brine to the saturation point (about 30% concentration). This is the feed
to the proposed process.
Hint: The material balance on this concentrator is carried out as follows:

Total balance F = D + B

The component mass balance on the salt can be obtained as follows:

15 ´ 106 (0.07) = B(0.3)

Therefore, B = 3.5 × 106 GPD is the rate of concentrated brine to be pro-

cessed next for the chemical conversion step, and a distillate rate of the
freshwater is obtained by using the equation D = 11.5 × 106 GPD.

F Concentrator/
evaporator

B
216 Chemical Engineering Primer with Computer Applications

The main objective in this case study is to figure out how much chemical
products we produce for a given feed input of brine. Also, it is important
to calculate how much ammonia and carbon dioxide we consume in the
process.
3. Comment on the proposed process as compared to the traditional water
desalination.

10.6 CASE STUDY 5: APPLICATIONS OF DIFFERENTIAL

EQUATIONS
10.6.1 introduction
Many problems in engineering and science can be formulated in terms of dif-
ferential equations. A differential equation is an equation involving a relation
between an unknown function and one or more of its derivatives. Equations
involving derivatives of only one independent variable are called ordinary dif-
ferential equations. Since there are relatively few differential equations arising
from practical problems for which analytical solutions are known, one must resort
to numerical methods.

10.6.2 ProBlem statement

Soap is prepared through a reaction known as saponification. In saponification, tal-
low (fats from animals such as cattle) or vegetable fat (e.g., coconut) is reacted with
potassium or sodium hydroxide to produce glycerol and fatty acid salt known as
soap. The soap is separated from the glycerol through precipitation by the addition
of sodium chloride. Water layer on top of the mixture that contains dissolved sodium
chloride is drawn off the mixture as a waste. This method of soap making is still
being practiced in many villages in developing countries where the price of mass-
produced soap maybe too expensive for the average villager.

10.6.3 ProPosed aPProacH

Two chemical engineering students used their knowledge of saponification acquired
in their organic chemistry class to organize and produce homemade soap. The
local  ordinance requires that the minimum concentration level for sodium chlo-
ride waste in any liquid that is discharged into the environment must not exceed
11.00 g/L. Sodium chloride laden liquid water is the major waste of the process.
The company has only one 15 L tank for waste storage. On filling the waste tank,
the tank contained 15 L of water and 750 g of sodium chloride. To continue produc-
tion and meet the local ordinance, it is desired to pump in freshwater into the tank
at the rate of 2.0 L/min, while waste saltwater containing 25 g of salt/L is added at
the rate of 1.5 L/min. To keep the solution level at 15, 3.5 L/min of the waste is
discharged.
A sketch in Figure 10.8 is given, where A represents the waste stream from
the process, B is the freshwater stream, and C is the discharge stream to the
Case Studies 217

Stream A Stream B
1.5 L/min 2 L/min
25 g/L 0 g/L

Stream C
3.5 L/min
x1 g/L

FIGURE 10.8 Flow diagram for a saponification process.

environment. Here, it is assumed that as the two streams, A and B, enter into the
tank, instantaneously the chloride concentration in the tank changes to the exit
concentration, x1.
A material balance on sodium chloride is carried out for the tank system as
follows:

Rate of change in salt concentration with time = Input − Output (10.6.1)

dx1
= (25 g/L)(1.5 L/min) + (0 g/L)(2 L/min ) - (x1 g/L)(3.5 L/min) (10.6.2)
dt

dx1
+3.5x1 = 37.5 (10.6.3)
dt

Divide both sides by 3.5

1 dx1 dx
+ x1 = 0.286 1 + x1 = 10.7 (10.6.4)
3.5 dt dt

By using an integrating factor (IF) for Equation 10.6.4, solution is found to be

X1 = 10.7 + C e - t/0.286

For the initial boundary conditions, at t = 0, the salt concentration in the tank was
given as 750 g/15 L (50 g/L) or at t = 0, x1(0) = 50 g/L.
Therefore,

50 = 10.7 + C, or C = 50 - 10.7 = 39.3

218 Chemical Engineering Primer with Computer Applications

The final solution is given by

X1 = 10.7 + 39.3e - t/0.286

Checking:
As t increases, e−t → 0, and X1 → a, value = 10.7
And at t = 0, e−t = 1, and x1 → a, value = 50

10.6.4 discussions
• Using Equations 10.6.3 and 10.6.4, numerically determine how the concen-
tration of the discharged salt changes with time.
• Plot a graph for the relationship that represents your solution.
• How long did it take to achieve the minimum required local specifications?
At steady state, what is the concentration of salt being discharged from this
local soap factory? (Kaw and Kalu, 2011)

10.7 CASE STUDY 6: REACTIVE DISTILLATION

10.7.1 introduction
Reactive distillation (RD) is a process in which a catalytic chemical reaction and
distillation (fractionation of reactants and products) occur simultaneously in one
single apparatus. Separation of the product from the reaction mixture does not need
a separate distillation step, which saves energy (for heating) and materials. Reactive
distillation or catalytic distillation combines reaction and distillation into a single
column.
This technique is especially useful for equilibrium-limited reactions such
as esterification and ester hydrolysis reactions. Conversion can be increased far
beyond what is expected by the equilibrium due to the continuous removal of reac-
tion products from the reactive zone. This helps reduce capital and investment costs
and may be important for sustainable development due to a lower consumption of
resources.

10.7.2 oBjective
In comparing the traditional versus the reactive distillation methods, such as in the
production of methyl acetate, for example (Figure 10.9), the latter methods have
the following advantages:

• Improve selectivity
• Reduce by-products
• Prevent pollution
• Reduce energy use
• Handle difficult separations
• Avoid separating reactants
Case Studies 219

Condenser

Product 1
Rectification
Feed 1 section

Catalyst
Reaction zone
(extractive distillation zone)

Feed 2
Stripping
section

Evaporator

Product 2

FIGURE 10.9 Example of production of methyl acetate.

• Eliminate/reduce solvents
• Enhance overall rates
• Beat low equilibrium constants

10.7.3 discussion
The introduction of a separation process side by side in the reaction zone, or vice
versa, could lead to many difficulties in reactive distillation process. Give examples
of some of these problems. On the other hand, some of the merits that apply in the
case of reactive distillation could be applied to other aspects in many unit operations.
Give examples of similar cases, especially in surface oil operations that involve crude
oil and gas field treatment and processing (see texts by the author in bibliography).

REFERENCES
CACHE Corporation, CACHE Process Design Case Studies, The CACHE Corporation, 2016.
http://cache.org/super-store/cache-process-design-case-studies.
The Essential Chemical Industry (ECI), Case Studies in Chemical Engineering, Imperial
Chemical Industries (ICI), London, U.K., 1970–1979.
Kaw, A. and Kalu, E.E., Numerical Methods with Applications: Abridged, 2nd edn.
Tampa, FL: University of South Florida, March 2011.
Appendix A: Application
Problems
A.1 SECTION I (CHAPTERS 1 AND 2)
This set of problems is aimed to go hand in hand with the materials covered in
Chapters 1 and 2. The solution of some simple problems could be done either manu-
ally or using MATLAB® or Excel. It involves basic conversion of units and other
fundamental calculations.

1. The heat capacity of sulfuric acid is measured in cal/(g · mol)(°C). It is given

by

Heat capacity = 33.25 + 3.727 ´ 10 -2 T ,

where T is in °C
It is required to have the heat capacity expression in terms of °R.
2. A tank contains CO2 is used to supply a system with CO2. The pressure
gauge reads 50 psi. Determine the absolute pressure in the tank, in psi, if
the barometer reads 28.0 in. · Hg.
3. Calculate the gauge pressure in lbf/in.2 at a depth of 4.0 miles below the sea
surface. Assume the water temperature is 60°F and the specific gravity is
1.042.
4. Calculate the diameter of a pipeline handling 12,000 bbl of oil/h assuming
the velocity of flow in the pipe line is 5 ft/s (1 ft3 = 0.413 barrel).
5. Polonium has a half-life of 140 days. Starting with 50 g today, how much is
left after 200 days?

Amount left = Initial amount(0.5)half-life time

6. Find the volume of a tubular reactor, with a residence time of the reaction
being 60 s. The input feed flow rate to the reactor is 400 ft3/min.
7. What is the weight of air in a room having a volume of 2000 ft3 at T = 80°F
and P = 750 mm Hg.
8. In one of your experiments in unit operations laboratory, a reading of
400 cm3/min was measured. How do you covert it to in.3/h?
9. In experiment in problem 8, the pressure gauge reads 12 psi and the
atmospheric pressure is 14 psi. What is the absolute pressure in this
experiment?

221
222 Appendix A: Application Problems

10. What will be the concentration of O2 dissolved in water at 298 K when the
solution is in equilibrium with air at 1 atm total pressure?
Hint: Apply Henry’s law, pA = HxA,

where
H is the Henry’s constant = 4.38 × 104 atm/mol fraction
pA is the partial pressure of O2 in air, which is taken as 0.21 atm.

11. Find the density of methane gas at T = 70°F and P = 760 mm Hg, by using
the gas equation.
12. An orifice meter is used to measure flow rates in a pipeline. Given the fol-
lowing relationship,

u = C [ DP/ ]0.5,

where
u is the fluid velocity
ΔP is the pressure drop
ℓ is the density
C is a constant

What are the dimensions of C in the cgs system of units?

13. Crude oil when produced may contain water. For the separation of water-
drops from oil, it was found that V = f (d, T), where V is the settling veloc-
ity of the waterdrop, d is the drop diameter (in.), and T is the operating
temperature. In charge of this separator, you are asked to plot the following
data to indicate the relationship between these variables (hint: T versus V).
Notice that V increases (separation is better) with higher T and larger d.
Settling Velocity, V (ft/h)
Values of V at different T and for different d are as follows:

T (°F) d = 0.1 d = 0.15 d = 0.2

110 5 16 28
130 8 18 30
160 10 20 35

14. Analyze the following equation for dimensional consistency: P = g × h,

where g is the gravitational acceleration and h is the height of the fluid.
15. Hydrogen is produced by water electrolysis: 2H2O → 2H2 + O2.
Calculate how much hydrogen is produced from 800 kg of water. Hint: Use
mole balance.
Appendix A: Application Problems 223

A.2 SECTION II (CHAPTERS 3 AND 4)

This set of problems may require using MATLAB or Excel to solve them as dem-
onstrated before. It is up to the instructor to assign these problems chapterwise, as
application exercises while covering lectures.

16. A chemical plant located at the base of a mountain (about 300 ft) has to
dispose of its CO2 by-product. An engineer proposed a unique method for
absorbing the CO2 in water; water is then lifted up the mountain. The CO2
was then vented to the atmosphere and water is recirculated as shown in
the diagram. Assume that CO2 is to be absorbed in water at a CO2 partial
pressure, pCO2 , of 10 psi above that required to lift the water up to the top of
the mountain (300 ft). Calculate the amount of water required to dispose of
5000 ft3 of CO2 at STP.
Hint: (a) Calculate pCO2 to take care of the pressure head for uplifting.
(b) Apply Henry’s law to find the X CO2 absorbed in water: p = Hx.

CO2 venting
Top of the mountain

Water

CO2 absorbed
in water

Chemical
plant

17. For the flash separation of a multicomponent mixture, show that Yi = Zi /

[(1/K i) – (V/F)(1/K i−1)].

V, yi

Flash
Distill
F, Zi

L, xi

Hint: Make material balance (MB) and eliminate xi using yi = K ixi.

224 Appendix A: Application Problems

18. A stream of air is passing through a tube. Its flow rate, F, is unknown. In
order to determine the value of F, another gas, CO2, is introduced in the
tube at the entrance point, as shown in the diagram at a rate = 1 ft3/s. The
composition of the effluent stream (air + CO2) that exits the tube was mea-
sured and found to have 0.5% CO2 by volume. Calculate F, using compo-
nent MB on CO2.

CO2
Air + CO2
Tube
Air, feed

19. Seawater is desalinated using multistage flash distillation. Assuming the

concentration of the seawater is C0, the feed rate is 1000 gal/min, and the
desalination process will produce 50% of the feed as top desalinated prod-
uct and the balance as bottom product, figure out the concentration of this
product, as a ratio of C0.
20. A tank containing 8 ft3 of a mixture of water and acetic acid has a valve
at the bottom. If 40% of this mixture is acetic acid, how much of this
mixture should be drained from the tank (through the valve) and to be
replaced by pure acid in order to have the new concentration of the mix-
ture be 60%?
Hint: Make an MB on the acid. Let X be the amount of mixture to be
drained and set up one algebraic equation in one unknown, X.
21. A continuous distillation column is to separate a mixture of two compo-
nents A and B at atmospheric pressure. A feed is entering the column
(bubble-point feed) at F moles/h, with X FA as feed composition. Products
are XDA and XBA. Reflux ratio is R = L0/D, where L0 enters the column at
T°C.
If hF, hD, Hv, and hw are the enthalpy of feed, enthalpy of distillate, enthalpy
of top vapor, and enthalpy of bottom product, respectively, show how you
calculate Qc and QR with the help of the diagram shown.

QC
D, hD, XD
F, hf

QR
B, hB, XB

22. Applying the Newton’s law of cooling, dT/dt = −k(T−30), where the tem-
perature of moving air is 30°C, T is the temperature of the substance at time
t minutes, and k is a constant, find the time necessary to cool a substance
from 100°C to 40°C, if the same substance cools from 100°C to 70°C in
15 min time.
Appendix A: Application Problems 225

23. Compute the bubble-point temperature (Tbp) at P = 2 atmosphere for the

three-component mixture given next, using the Newton’s method. Take the
first assumed value for Tbp = 150°F.

Component Ki Composition (xi)

1 K1 = 0.01T/P 0.333
2 K2 = 0.02T/P 0.333
3 K3 = 0.03T/p 0.333

24. Estimate the average density of a water/ethanol mixture, to be prepared for

distillation at different water compositions knowing that

Water density = 1000 kg/m 3

Ethanol density = 780 kg/m 3

Mixture density = Xwater (Water density) + Xethanol (Ethanol density)

25. A pilot plant distillation column is used to strip alcohol from a feed stream
of ethyl alcohol and water, containing 1.5 mole% alcohol. The following
conditions apply:

Feed rate = 16 lb × mol/h,

where the distillate contains 87% alcohol and the bottom product contains
0.05 % alcohol. Calculate all stream flow rates.
26. At 1000°C and a total pressure of 30 atm, the equilibrium in the reaction

CO2 (g) + C(s) ® 2CO(g)

is such that 17 mole% of the gas is CO2. What percent will be CO2 if the
total pressure is 20 atm instead of 30 atm?
27. Draw a computer block diagram for solving flash separation problem by
trial and error.
28. Find the value of V/F for a feed consisting of 10, 20, 30, and 40 mole% of
propane, butane, pentane, and hexane, respectively, to be flashed at 200°F
and 100 psia. The corresponding values of K i for the hydrocarbons are 4.5,
1.8, 0.75, and 0.37 (in the same order).
29. Calculate the temperature and composition of a liquid in equilibrium with
a gas mixture containing 10.0 mole% benzene, 10.0 mole% toluene, and the
balance nitrogen (which may be considered noncondensable) at 1 atm. Is the
calculated temperature a bubble-point or dew-point temperature?
30. Under limited conditions, volume balance can be applied to liquids in con-
junction with a mass balance. Non–polar mutually–soluble liquids in gen-
eral are blended so that the volume is approximately equal to the sum of the
226 Appendix A: Application Problems

liquid volumes of the components. Find the yields of light and heavy cuts
that can be produced from 100 gal of gas oil under the given conditions:

L, ρ = 0.8

Gas oil: ρ = 0.85

H, ρ = 0.93

31. During a chemical reaction, substance A is converted into B at a rate pro-

portional to the square of the amount of A:

A ® B.

If at time t = 0, 60 g of A is present, and then after 1 h (t = 1), only 10 g of A

remains unconverted, find how much of A is present after 2 h?
Hint: Let C be the amount of A present at any time. Solve the differential
equation: dc/dt = …
32. A mixture containing 45% benzene (B), 50% toluene (T), and 5% nitroben-
zene by mass is fed to a distillation column. The overhead stream consists
of 95% B and 4% T. The bottom product contains 90% T.
Assuming the feed rate is 2000 kg/h.
Calculate the overhead and bottom flow rates. Determine the mass flow
rates of B and T in the bottom product.
33. Write a program to estimate the physical properties for water in the range of
temperatures from 273 to 323 K.
Given
Density

r = 1200.92 - 1.0056T + 0.001084T 2

Conductivity

K = 0.34 + 9.278 * 10 -4 T

34. Make a table of (x vs. y) values for the three components such as ethanol,
water, and benzene, at T = 373.15 K. The vapor pressure of these three
components is calculated by (Note: Take 11 points for each component from
0 to 1)

æ 18.5242 - 3578.91 ö
Ethanol Peo = exp ç ÷
è T - 50.5 ø
Appendix A: Application Problems 227

æ 18.3036 - 3816.44 ö
Water Pwo = exp ç ÷
è T - 46.13 ø

æ 15.9008 - 2788.51 ö
Benzene Pbo = exp ç ÷
è T - 52.36 ø

where

K i = Pio /Pt

Pt = 760

yi = K i ´ xi

35. An ammonia synthesis converter receiving a total feed (T moles) consists of

H2 and N2 at a 3:1 ratio for the following reaction:

N 2 + 3H 2 ® 2NH 3

The total feed (T moles) is made up of fresh feed (F moles) + recycle stream
(R moles). The gross product (G moles) is 12% NH3 moles, which goes to a
separator, removing all NH3 and allowing recycled stream to return to the
convertor. For F = 100, calculate G and R.

A.3 SECTION III (CHAPTERS 5 THROUGH 9)

Similar to the other two parts, a set of application problems is presented. This set com-
prises many types of problems frequently encountered by chemical engineering students.

36. In a distillation train, a liquid hydrocarbon containing 20 mole% ethane,

40 mole% propane, and 40 mole% butane is to be fractionated into essen-
tially pure components as shown next.
On the basis of F = 100 moles, what is the value of P (in moles) and the
composition of stream A?
Ethane fraction Propane fraction
95% C2 99% C3
4% C3 1% C4
E 1% C4
P
1 2

F
Feed
20% C2 A
40% C3
Xp = ?
40% C4
B
XB = ?
Propane fraction
8.4% C3
91.6% C4
228 Appendix A: Application Problems

37. Equilibrium constants (k values) are needed for our distillation calcula-
tions, as was explained earlier. Write a program to calculate the vapor
pressure for the following system and to calculate and tabulate its k
values.

æ 14.2724 - 2945.47 ö
P1 = exp ç ÷
è T + 224 ø

æ 14.2043 - 2972.64 ö
P2 = exp ç ÷
è T + 2 09 ø

Temperature range = 75°C–125°C. Use 11 points for temperature

Pt = 101.3

Pi
Ki =
Pt

38. Water at 320 K is pumped through a 40 mm ID pipe through a length of

150 m in a horizontal direction and up through a vertical height of 12 m
at a rate of 2.16 m3/h. In the pipe there are fittings equivalent to 260 pipe
diameters. What power must be supplied to the pump if it is 60% efficient?
Take the value of fanning friction factor as 0.008. Water viscosity is 0.65 cp
and density = 1 gm/cc.
39. As a leader in your group, in charge of process design, you are asked to
draw a simplified process flow diagram for the production of hydrochloric
acid, HCl, as described next:
It is manufactured by the reaction of NaCl and H2SO4. The raw materi-
als are fed to a furnace where they are mixed and indirectly heated. The
acid and salt react to give HCl gas, which then flows to heat exchangers to
be cooled by water and then passes successively to gas-absorption towers.
The gas enters the bottom of the first tower, leaves at the top, and flows into
the bottom of the second tower. Water is fed to the top of the second tower,
while the dilute HCl acid collected from the bottom of the same tower is
supplied to the top of the first tower. Strong HCl acid is withdrawn at the
base of the first tower and pumped to a storage tank. Waste gas is with-
drawn by a blower at the top of the second tower.
40. Water at the rate of 150 lbm/min is heated from 100°F to 160°F using oil
with a specific heat of 0.45. A countercurrent double-pipe heat exchanger
is used. The oil enters at 230°F and leaves at 150°F. Assuming U0 is
60 Btu/h · ft2 · °F, calculate the heat exchanger area.
41. One face of a copper slab is maintained at 1000°F and the other face is at
200°F. How much heat is conducted through the slab per unit area?
Given: The slab is 3 in. thick and k = 215 Btu/h · ft · °F.
Appendix A: Application Problems 229

T1 = 1000°F q
3 in.

T2 = 200°F

42. A solution of ethyl alcohol containing 8.6% alcohol by weight is fed at

the rate of 5000  kg/h to a continuous fractionating column operating at
atmospheric pressure. The distillate, which is the desired product, contains
95.4% alcohol by weight and the residue from the bottom of the column
contains 0.1% alcohol by weight. Calculate the following:
i. The mass flow rates of the distillate and residue in kg/h
ii. The percentage loss of alcohol
43. A feed of 50 mole% hexane and 50 mole% octane is fed into a pipe still
through a pressure reducing valve and then into a flash disengaging cham-
ber. The vapor and liquid leaving the chamber are assumed to be in equi-
librium. If the fraction of the feed converted to the vapor is 0.5, find the
compositions of the top and bottom products. The following table gives the
equilibrium data for this system:

Mole fractions of hexane in liquid x 1.00 0.69 0.40 0.192 0.045 0.00
Mole fractions of hexane in vapor y 1.00 0.932 0.78 0.538 0.1775 0.00

44. A continuous fractionating column is to be designed for separat-

ing 10,000  kg/h of liquid mixture containing 40 mole% methanol and
60 mole% water into an overhead product containing 97 mole% methanol
and a bottom product having 98 mole% water. A mole reflux ratio of 3 is
used. Calculate (i) moles of overhead product obtained per hour and (ii)
number of ideal plates and location of the feed plate if the feed is at its
bubble point.
Equilibrium data are as follows:

x 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

y 0.417 0.579 0.669 0.729 0.78 0.825 0.871 0.915 0.959

where
x is the mole fraction of methanol in liquid
y is the mole fraction of methanol in vapor

Given: Feed rate = 10,000 kg/h, zF = 0.4, xD = 0.97, XW = 0.02, R = 3

230 Appendix A: Application Problems

45. A saturated liquid mixture containing 60 mole% benzene and 40 mole%

toluene is to be distilled continuously into a distillate product containing
90 mole% benzene and the bottom product containing 5 mole% benzene.
The fractional distillation column will operate at approximately constant
pressure of 1 atm. The reflux ratio is 2. How many theoretical plates must
the column have if the feed is introduced into the eighth plate? Equilibrium
data are as follows:

x 0 0.017 0.075 0.13 0.211 0.288 0.37 0.411 0.581 0.78 1

y 0 0.039 0.161 0.261 0.393 0.496 0.591 0.632 0.777 0.9 1

Given: ZF = 0.6, XD = 0.9, XW = 0.05, R = 2, XD/(R + 1) = 0.9/(2 + 1) = 0.3

Feed is saturated liquid at eighth plate.
46. Heat loss/gain takes place in a pipe carrying hotter/colder fluid than ambi-
ent temperature. Insulation reduces the heat loss to surroundings. Heat loss
depends upon the number of factors like insulation thickness, ambient tem-
perature, and wind speed. This shows how to calculate heat loss from an
insulated pipe and a bare pipe to surroundings.
Problem statement: A carbon steel pipe, 3 in. diameter, is carrying hot oil
at 180°C and insulated with 50  mm thick calcium silicate. Insulation is
cladded with a sheet with surface emissivity of 0.9. Ambient temperature is
28°C and wind velocity is 3.5 m/s.
Calculate the surface temperature and heat loss from insulated and bare
pipe.
Fluid
Air

Insulation D1 D2 D3

Pipe

The overall heat transfer coefficient of an insulated pipe is defined as the

follows:

1
U=
æD ö æ D3 ö
D3 × ln ç 2 ÷ D3 × ln ç D ÷
D è D1 ø+ è 2ø + 1
+
D1 × h in 2 × k PIPE 2 × k INSULATTION h AIR

where
k PIPE and k INSULATION are the thermal conductivities of the pipe and
insulation
hin is the heat transfer coefficient for fluid flowing in pipe
hAIR is the heat transfer coefficient due to air flowing outside the pipe
Appendix A: Application Problems 231

The first two terms of the denominator in this equation are generally smaller
compared to the remaining terms and can be neglected. For this example,
the first term due to pipe fluid is ignored.
47. An evaporator is fed with 10,000 kg/h of a solution containing 1% solute
by weight. It is to be concentrated to 1.5% solute by weight. The feed is
at a temperature of 37°C. The water is evaporated by heating with steam
available at a pressure of 1.34 atm absolute, corresponding to a temperature
of 108.3°C. The operating pressure in the vapor space is 1 atm absolute.
Boiling point elevation and other effects can be neglected. The conden-
sate leaves at the condensing temperature. All the physical properties of the
solution may be taken to be the same as that of water. What is the quantity
of steam required per hour?
Data
Enthalpy of feed = 38.1 kcal/kg
Enthalpy of solution inside the evaporator (at 100°C) = 98 kcal/kg
Enthalpy of vapor at 100°C = 644 kcal/kg
Latent heat of vaporization of steam = 540 kcal/kg
48. Methanol is produced by the following reaction:

CO + 2H 2 ® CH 3OH

In the reactor, 15% of the CO is converted to methanol. Materials exit the

reactor and flow to a separator to produce liquid methanol as a product. A
recycle of unreacted gases is done. A purge stream is done for the impuri-
ties as shown in the diagram.
Calculate the amount of feed, F1, recycle, F2, and purge, F4. Assume 10,000
mol/h of methanol product, F3.

F4 33% CO, 66% H2, 1% impurities

F2
Reactor Separator
F1 33% CO, 66% H2, 1% impurities F3

49. A triple-effect evaporator is concentrating a liquid. Temperature of the

steam to the first effect is 227°F (about 5 psig). Vacuum on the last effect is
26 in. (125°F).
Values of the overall heat transfer coefficients are 500, 400, and 200 for
the first, second, and third effect, respectively. What are the approximate
temperatures at which the liquid will boil in the first and second effect?
Hint: Temperature drops will be approximately inversely proportional to
the heat transfer coefficient.
50. Write a program to calculate the vapor pressure for the following system
and to calculate and tabulate its k values.
232 Appendix A: Application Problems

æ 14.2724 - 2945.47 ö
P1 = exp ç ÷
è T + 224 ø
æ 14.2043 - 2972.64 ö
P2 = exp ç ÷
è T + 209 ø

Temperature range = 75°C–125°C. Use 11 points for temperature.

Pt = 101.3

Pi
Ki =
Pt

A.4 ANSWERS TO PROBLEMS

1. Heat capacity = 23.06 + 2.07 × 10 −2 TR.
2. Pabs = 13.75 + 50 = 63.75 psi.
3. P = 9533 lbf/in.2
4. D = 0.59 ft.
5. N(t) = 50(1/2)200/140 = 50(1/2)1.4286 = 50 × 0.3715 = 18.575 g.
6. V = (q)(θ) = (400 ft3/min)(60 s)(1/60) (s/min) = 400 ft3.
7. Mass of air = 2000 ft3 × 0.0735 lb/ft3 = 147 lb.
8. 1608 in.3/h.
9. 26 psi.
10. xA = (0.21)/4.38 × 104 = 0.0479 × 10 −4.
11. ρ = 0.0414 lb/ft3.
12. Use cgs units.
13. Plot v versus D using T as a parameter.
14. Use basic units.
15. 88.9 kg hydrogen is produced from 800 kg water.
16. Quantity of water = 8730 lb = 3960 kg.
17. Use simple substitution.
18. F, feed rate = 11,940 ft3/min.
19. Solve for CB = (1000/500)C0 = 2C0.
20. X = 8/3 ft3.
21. Qr (heat duty for reboiler) = DhD + BhB + V1Hv − D[hD + (L0/D)] − (F)hf.
22. t = 52 min.
23. Follow the solution of Example 4.1.
24. Solution is done through MATLAB.
25. D = 0.267 lb × mole/h
B = 15.733 lb × mole/h.
26. Mole% CO2 = (2.55/20)100 = 12.75.
27. Solution follows the Newton–Raphson procedure.
28. V/F is found = 0.1765.
29. Solution is similar to the one given in Example 4.4.
Appendix A: Application Problems 233

30. Solving for L = 61.5 gal and H = 38.5 gal.

31. After, 2 h, the concentration, c = 60/[(5)(2) + 1] = 5.45 g.
32. D = 930.2 kg/h, B = 1069.8 kg/h, wB = 16.3 kg/h, wNB = 90.7 kg/h.
33. Solution is done through MATLAB.
34. Solution is done through MATLAB.
35. Solution is done through Excel.
36. Composition of stream A is found by doing a T M B around column 1.
37. Solution is done through MATLAB.
38. Power required for pumping = 0.0006 ´ 133443.2 / 0.6
= 133.4 W = 133.4 / 736 HP = 0.181 HP.
40. A, is readily calculated = Q/UΔTLM = 540,000/[60 × 59.6] = 151 ft2.
41. Q = 3.9 × 106 w/m2.
42. Percentage loss of ethanol = 100 × (4.554 /430) = 1.06.
43. Composition of top product = yD = 69% hexane.
44. D = 169.492 kmol/h, and the number of theoretical plates is estimated uti-
lizing the McCabe–Thiele graphical construction method and found to be
equal to 6.8. And the location of the feed plate is fifth plate (counting from
the top).
45. The equilibrium data are plotted utilizing McCabe–Thiele method; the
number of theoretical plates is found to be = 11 for the feed introduced at
the eighth plate.
46. Q = (Ts – Ta)/[R1 + R2] = (355 − 82.5)/1.8 = 151.4 Btu/h.
Compare the Q lost for bare pipe to the one with insulation.
47. S = 4479.6 kg/h, that is, the steam required = 4479.6 kg/h.
48. Using MATLAB, F1, F2, and F4 in mol/h are found to be x = 33,333.3333,
168,383.8384, and 3,333.3333, respectively.
49. The boiling point in the first effect will be = 206.5° and in the second
effect = 181.5°.
50. Problem is attempted using MATLAB.
Appendix B: Mathematical
Methods and Review Notes
B.1 USEFUL CONSTANTS
B.1.1 universal matHematical constants
A mathematical constant is a special number, usually a real number, which is
significantly interesting in some way (Weisstein, 2011). Constants arise in many
areas of mathematics, with constants such as e and π occurring in such diverse con-
texts as geometry, number theory, and calculus.
It is a diverse matter; what it means for a constant to arise naturally and what
makes a constant interesting is ultimately a matter of taste, and some mathematical
constants are more notable for historical reasons than for their intrinsic mathemati-
cal interest.

Children Face Tough Children Face Tough

Children Face Tough Children Face Tough
Children Face Tough Children Face Tough
Children Face Tough Children Face Tough
Children Face Tough Children Face Tough
Children Face Tough Children Face Tough
Children Face Tough Issues Children Face Tough
Children Face Tough Children Face Tough

235
236 Appendix B: Mathematical Methods and Review Notes

B.1.2 values oF gas constants (jensen, 2003)

8.3144621(75) J/K · mole
0.08205746(14) L · atm/K · mole
1.9858775(34) cal/K · mole
8.3144621(75) L · kPa/K · mole
8.3144621(75) m3 · Pa/K · mole
8.205746 × 10 −5 m3 · atm/K · mole
82.05746 cm3 · atm/K · mole
62.36367(11) L · Torr/K · mole
6.132440(10) ft · lbf/K · g · mole
10.73159(2) ft3 · psi/°R · lb · mole
0.7302413(12) ft3 · atm/°R lb · mole
1.31443 ft3 · atm/K · lb · mole
998.9701(17) ft3 · mm Hg/K · lb · mole
1.986 Btu/lb · mole · °R

B.2 ROOT-FINDING METHODS

Root finding is the determination of solutions to single-variable equations or to sys-
tems of n equations in n unknowns (provided that such solutions exist). The basics of
the method revolve around the determination of roots.
Appendix B: Mathematical Methods and Review Notes 237

B.2.1 introduction
Two approaches can be pursued to seek a solution: analytical and numerical.
An analytical solution to an equation or system is a solution that can be arrived at
exactly using some mathematical tools. For example, consider the function y = ln (x),
graphed in the following.

1 2 3 4 5

–1

–2

–3

The root of this function is, by convention, when y = 0 or when this function
crosses the x-axis. Hence, the root will occur when ln (x) = 0 ≥ x = e0 = 1.
The answer x = 1 is an analytical solution because through the use of algebra,
we were able to come up with an exact answer. On the other hand, attempting to
solve other equations could be hard to achieve. In such cases, it is necessary to
seek a numerical solution, in which guesses are made until the answer is close
enough.

B.2.2 numerical root-Finding metHods–algoritHms

A root-finding algorithm is a numerical method, or algorithm, for finding a value
x such that f(x) = 0, for a given function f. Such an x is called a root of the
function.
Root finding methods are classified into:
238 Appendix B: Mathematical Methods and Review Notes

Bisection

Bracketing
methods Regula falsi

Interpolation

Newton’s

Open
Secant
methods

Interpolation

Combination Brent’s

Three methods are described briefly:

1. Bisection method
2. Newton–Raphson method (Tangent method)
3. Secant method

Roots can be simple or multiple (p. 66)

x* is a root of f having multiplicity q if

f (x) = (x – x*)q g(x) with g(x*) ≠ 0
f (x*) = f ΄(x*)=…= f (q–1)(x*) = 0 and f (q) (x*) ≠ 0

Simple root Double root

Appendix B: Mathematical Methods and Review Notes 239

Proof:
Use theory
x = cos x
All roots of x – cos x = 0 lie in the interval [–1,1] |x|=|cos x|≤1

0.5 f(x) = x – cos x Three rules

x
Use graphics 0
1. Graph the function
0.5 1
–0.5 2. Make a graph of the function
–1 3. Make sure that you have made
a graph of the function

Difficult cases:

0, 1 or 2 roots? Many roots

Pole

Bisection traps a root in a shrinking interval

Bracketing-interval theorem
If f is continuous on [a,b] and f(a) . f(b) < 0 then f has at least one zero in (a,b).

Bisection method
a+b
Given a bracketing interval [a,b], compute x = and sign( f (x));
2
repeat using [a,x] or [x,b] as new bracketing interval.
function x=bisection(f,a,b,tol)
sfb = sign(f(b)); >> f = @(x) x–cos(x);
width = b–a; >> bisection(f,0.7,0.8,1e–3);
disp(‘ a b sfx’) a b sfx
while width > tol 0.70000000 0.80000000 1
width = width/2; 0.70000000 0.75000000 –1
x = a + width; 0.72500000 0.75000000 –1
sfx = sign(f(x)); 0.73750000 0.75000000 1
disp(sprintf(‘%0.8f %0.8f %2.0f’, [a b sfx])) 0.73750000 0.74375000 1
if sfx == 0, a = x; b = x ; return 0.73750000 0.74062500 –1
elseif sfx == sfb, b = x; 0.73906250 0.74062500 1
else, a = x; end
end

Bisection is slow but dependable.

Advantages

• Guaranteed convergence
• Predictable convergence rate
• Rigorous error bound
240 Appendix B: Mathematical Methods and Review Notes

Disadvantages

• May converge to a pole

• Needs bracketing interval
• Slow

Newton – Raphson method uses the tangent

Iteration formula

f(xk)
xk+1 = xk –
f΄(xk)

x2 x1 x0

function x=newtonraphson(f,df,x,nk)
disp(‘k x_k f(x_k) f’’(x_k) dx’)
for k = 0 :nk
dx = df(x)\f(x);
disp(sprintf(‘%d %0.12f %9.2e %1.5f %15.12f’,[k,x,f(x),df(x),dx]))
x = x – dx;
end

>> f = @(x) x–cos(x); df = @(x) 1+sin(x);

>> newtonraphson(f,df,0.7,3);
k x_k f(x_k) f’(x_k) dx
0 0.700000000000 –6.48e–02 1.64422 –0.039436497848
1 0.739436497848 5.88e–04 1.67387 0.000351337383
2 0.739085160465 4.56e–08 1.67361 0.000000027250
3 0.739085133215 2.22e–16 1.67361 0.000000000000

Secant method is derivative-free

Iteration formula
f (xk )
xk+1 = xk –
f (xk ) – f (xk –1)
xk – xk –1 x2 x1 x0

function xx = secant(f,xx,nk)
disp(‘k x_k f(x_k)’)
ff = [f(xx(1)), f(xx(2))];
>> f = @(x) x–cos(x);
h = 10*sqrt(eps); >> secant(f,[0.7 0.8] , 6);
for k = 0 : nk
disp(sprintf(‘%d %17.14f %14.5e’,... k x_k f(x_k)
[k,xx(1),ff(1)])) 0 0.70000000000000 –6.48422e–02
if abs(diff(xx)) > h 1 0.80000000000000 1.03293e–01
df = diff(ff)/diff(xx); 2 0.73856544025090 –8.69665e–04
else 3 0.73907836214467 –1.13321e–05
df = (f(xx(2)+h)–ff(2))/h; 4 0.73908513399236 1.30073e–09
end 5 0.73908513321516 –1.77636e–15
xx = [xx(2), xx(2)–ff(2)/df]; % update xx 6 0.73908513321516 0.00000e+00
ff = [ff(2), f(xx(2))]; % update ff
end
Appendix B: Mathematical Methods and Review Notes 241

B.3 TIPS ON SOLVING PROBLEMS

B.3.1 matHematical modeling
The basic problems that we face in sciences and engineering, as far as mathematical
modeling is concerned, fall into three main categories:

1. Equilibrium problems: This type of problems is recognized as steady state,

where a solution does not change with time.
2. Eigenvalue problems: This type of problems is recognized as extensions of
equilibrium problems in which critical values of certain parameters are to
be determined in addition to the corresponding steady-state configuration.
3. Transient, time-varying, or propagation problems: This type of problems
is concerned with predicting the subsequent behavior of a system from the
knowledge of the initial stage.

Mathematical treatment involves four basic steps:

Formulation Solution Interpretation Refinement

Formulation step
may result in:

An algebraic eq., difference eq.,

differential eq., integral eq., or a
combination of these.

B.3.2 tHe role oF syntHesis and analysis

In handling problems in the chemical process industry, two stages are usually
involved: synthesis and analysis. Synthesis is the development and the creation of
a new idea, as demonstrated in process design in Chapter 9. Analysis, on the other
hand, confirms or rejects new ideas based on a feasibility study by subjecting them
to careful scrutiny to see if they obey or conflict the laws of physics and chemistry.
As explained earlier, the analysis process comprises the formulation process and
the development of the various equations, and their subsequent solutions for the
unknown variables.

REFERENCE
Jensen, W.B. The universal gas constant R, Journal of Chemical Education 80(7): 731,
July 2003.
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html. Retrieved April 13, 2011.
Appendix C:
Conversion Tables
Common Engineering Design Conversion Factors
Given Equivalent Value Unit of Measure
Length [L]
Foot (ft) 0.304800 Meter (m)
Inch (in.) 25.4000 Millimeter (mm)
Mile (mi) 1.609344 Kilometer (km)
Area [L]2
ft2 0.092903 m2
in.2 645.16 mm2
in.2 6.45160 cm2
Volume [L]3 and capacity
in.3 16.3871 cm3
ft3 0.028317 m3
ft3 7.4805 Gallon
ft3 28.3168 Liter (L)
Gallon 3.785412 Liter
Energy, work, or heat [M] [L]2 [t]−2
Btu 1.05435 kJ
Btu 0.251996 kcal
Calories (cal) 4.184* Joules (J)
ft · lbf 1.355818 J
ft · lbf 0.138255 kgf · m
hp · h 2.6845 MJ
kWh 3.600 MJ
m · kgf 9.80665* J
N·m 1 J
Flow rate [L]3 [t]−1
ft3/min 7.4805 gal/min
ft3/min 0.471934 l/s
gal/min 0.063090 l/s
Force or weight [M] [L] [t]−2
kgf 9.80665* Newton (N)
lbf 4.44822 N
lbf 0.453592 kgf
(Continued)

243
244 Appendix C: Conversion Tables

Common Engineering Design Conversion Factors

Given Equivalent Value Unit of Measure

Fracture toughness
ksi · sqrt(in.) 1.098800 MPa sqr(m)
Heat content
Btu/lbm 0.555556 cal/g
Btu/lbm 2.324444 J/g
Btu/ft3 0.037234 MJ/m3
Heat flux
Btu/h · ft2 7.5346E−5 cal/s · cm2
Btu/h · ft2 3.1525 W/m2
cal/s · cm2 4.184* W/cm2
Mass density [M] [L]−3
lbm/in.3 27.68 g/cm3
lbm/ft3 16.0184 kg/m3
Power [M] [L]2 [t]−3
Btu/h 0.292875 Watt (W)
ft · lbf/s 1.355818 W
Horsepower (hp) 745.6999 W
Horsepower 550* ft · lbf/s
Pressure (fluid) [M] [L]−1 [t]−2
Atmosphere (atm) 14.696 lbf/in.2
atm 1.01325E5* Pascal (Pa)
lbf/ft2 47.88026 Pa
lbf/in.2 27.6807 in. H2O at 39.2°F
Stress [M] [L]−1 [t] −2
kgf/cm2 9.80665E−2* MPa
ksi 6.89476 MPa
N/mm2 1 MPa
kgf/mm2 1.42231 ksi
Specific heat
Btu/lbm · °F 1 cal/g · °C
Temperature
Fahrenheit (°F − 32)/1.8 Celsius
Fahrenheit °F + 459.67 Rankine
Celsius °C + 273.16 Kelvin
Rankine R/1.8 Kelvin
Thermal conductivity
Btu · ft/h · ft2 · °F 14.8816 cal · cm/h · cm2 · °C
Appendix C: Conversion Tables 245

C.1 ENERGY UNITS AND CONVERSIONS

1 Joule (J) is the MKS unit of energy, equal to the force of 1 N acting through
1 m.
1 Watt is the power of a Joule of energy per second.

Power = current × voltage (P = IV ).

1 Watt is the power from a current of 1 A flowing through 1 V.

1 kilowatt is a 1000 W.
1 kilowatt-hour (kWh) is the energy of 1 kW power flowing for 1 h (E = Pt ).

1 kWh = 3.6 × 106 or J = 3.6 million Joules.

1 cal of heat is the amount needed to raise 1 g of water 1°C.

1 calorie (cal) = 4.184 J .

(The calories in food ratings are actually kilocalories.)

A British thermal unit (Btu) is the amount of heat necessary to raise 1 lb of
water by 1 degree Fahrenheit (°F).

1 Btu = 1055 J (the mechanical equivalent of heat relation).

1 Btu = 252 cal = 1.055 kJ.

1 Quad = 1015 Btu (world energy usage is about 300 Quads/year, and United
States is about 100 Quads/year in 1996).
1 therm = 100, 000 Btu .
1000 kWh = 3.41 million Btu .

C.2 POWER CONVERSION

1 horsepower (hp) = 745.7 Watts

C.3 GAS VOLUME TO ENERGY CONVERSION

One thousand cubic feet of gas (Mcf) → 1.027 million Btu = 1.083 billion J =
301 kWh
1 therm = 100,000 Btu = 105.5 million J = 29.3 kWh
1 Mcf → 10.27 therms
246 Appendix C: Conversion Tables

C.4 ENERGY CONTENT OF FUELS

Coal 25 million Btu/ton
Crude oil 5.6 million Btu/barrel
Oil 5.78 million Btu/barrel = 1700 kWh/barrel
Gasoline 5.6 million Btu/barrel (a barrel is 42 gallons) = 1.33 therms/gallon
Natural gas liquids 4.2 million Btu/barrel
Natural gas 1030 Btu/ft3
Wood 20 million Btu/cord

C.5 CO2 POLLUTION OF FOSSIL FUELS

Pounds of CO2 per billion BTU of energy:
Coal 208,000 lb
Oil 164,000 lb
Natural gas 117,000 lb
Ratios of CO2 pollution:
Oil/natural gas = 1.40
Coal/natural gas = 1.78
Pounds of CO2 per 1000 kWh at 100% efficiency:
Coal 709 lb
Oil 559 lb
Natural gas 399 lb
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Index
A Black box models, see Empirical models
Boiler feed pumps, 85
Absolute pressure Bottom product, 124
example, 18 Boyle’s law, 9
gauge pressure and, 74–75 example, 15, 28
Absorption Bubble-point (BP) temperature
analytical methods, 154–156 defined, 24, 50
concepts, 148–149 determination, 51–52
defined, 119, 147 Excel, calculating by, 53
design approach, 149 Newton’s method, calculating by, 52–53
example, 152–154 Raoult’s law, 55–56
graphical methods, 150
material balance calculations, 151
role in natural gas field processing, 156–157 C
transfer unit concept for, 156 Cash recovery period, see Payout period
Absorption factor method, 155 Catalytic reactor, 174–175
Acetonitrile, Pxy diagram of, 64–65 Celsius temperature scale, 6
Acid–base reaction, 168 Centigrade temperature scale, see Celsius
Acid concentration, finding, 41–42 temperature scale
Algorithms, 36 Centimeter–gram–second (cgs) system, 3, 5
solved examples, 38 Centrifugal force, 83
Alternatives to storage of ammonia (case study), Charles’ law, 9
202–204 example, 15, 28
Amagat’s law, 13 Chemical desalting of brines (case study)
American engineering system, 5 consumption–production analysis, 212–214
American Petroleum Institute (API) process discussion and problem formulation,
pumps, 85 215–216
Analysis process, 241 methodology, 210–211
Analytical methods, 154–156 primary reaction, 211
Annual rate of return, 195 product formation reaction, 212
Annuity, 194–195 secondary reaction, 212
Antoine coefficients, 51 Solvay process and proposed process, 213
Antoine equation, 51 synthesis process with modifications, 212
Applications of differential equations (case Chemical engineering
study), 216–218 defined, xxvii
Arrhenius equation, 169 plant design, 188–189
Association for the Advancement of Modeling problems, solution, 45
and Simulation Techniques in unit operation, 19–20
Enterprises (AMSE), 48 unit process, 20
Avogadro’s hypothesis, 14 Chemical industry, 188
Axial flow pumps, 85 Chemical kinetics, see Reaction kinetics
A–Z chart for plant design, 190–191 Chemical plant, 21–22
engineering aspect of, 48
B Chemical plant, design of
A–Z chart for, 190–191
Bernoulli’s equation, 77, 87 chemical engineering, 188–189
flow direction, determination, 90 economics role (see Economics in
head form of, 78 plant design)
Binary distillation, 134–135 flow sheeting and flow diagram, 191
Bisection method, 239–240 other aspects, 191–192
Blackbody radiation, 107 proposed procedure, 189–190

251
252 Index

safety factors, 191, 192 Design problem in distillation, 130

scale-up practice, 191 Design variables for sizing piping, 23–24
Chemical process engineers, 21 Desorption, 119
Chemical process industry (CPI), 20–21 Dewatering process, 85
Chemical product engineers, 21 Dew-point (DP) temperature
Chemical pumps, 85 defined, 52
Chemical reactions examples, 54, 56–57
categories of, 27, 167–168 Differential equations, 216–218
equilibrium constant for, 24 Differential rate law, 165, 168–170
free energy of formation in, 180–181 Differential-stage contactors, 123
Chemical reactors Differentiation, example, 39
catalytic reactor, 174–175 Diffusional mass transfer, 20, 119
chemical equilibrium, using MATLAB®, 184 Diffusional unit operations, 21
design, 175–178 Discounted cash-flow rate of return (DCFR), 196
laboratory and industrial catalytic solved examples, 199–200
reactors, 173 Distillation
models, classified, 172 classification methods, 122
Circulator pumps, 85 column diameter, 144
Combustion of heptane, 30 concepts and principles, 120–123
Combustion reaction, 167 defined, 119
Common engineering design conversion factors, design problem, 130
243–244 flash distillation, 144–147
Compressible fluid, 70 McCabe–Thiele method (see McCabe–Thiele
Computational science, components, xxii method)
Computers, problem solving using, 46–47 overhead condensers, 125–126
Conceptual model, 49 physical models for, 131
Conduction, heat transfer by pillars for, 123–124
Fourier’s law, 97–98 rating (operational) problem, 130–131
solved examples, 99–101 reactive, 147
thermal conductivity, 96, 98 reboilers, 127
through hollow cylinder, 99 reflux and reflux ratio, 126–127
through solids in series, 99 shortcut methods (see Shortcut calculation
Consistency, 71 methods)
Consumption–production analysis, 212–214 units, features of, 124
Continuous stirred-tank reactor model Distillation columns
(CSTR), 174 design of, 129–131
Convective heat transfer example, 58
convective heat transfer coefficient, 102 number of trays, calculation of, 131
example, 103 rectification and stripping sections in,
fluid motion, 96 127, 130
methodology of calculation, 102 types, 125, 126, 128
natural convection vs. forced convection, 101 Distribution constant, 24, 147
Conversions Double displacement reaction, 168
energy units and, 245 DP temperature, see Dew-point temperature
gas volume to energy, 245
physical events, 24–25 E
power, 245
Countercurrent flow, 107, 108 Economic balance in piping, 80–81
CPI, see Chemical process industry Economics in plant design
Cross flow, 107 annuity, 194–195
Crude oil distillation, flow diagram for, xxiv FCI and total capital investment, 193–194
profitability analysis, 195–196
D Effective equilibrium curve (EEC), 139–140
Eigenvalue problems, 47, 241
Dalton’s law, 9–10, 50 Electromagnetic radiation, 106
Decomposition reaction, 167 Elementary numerical methods, applications
Derived units, 3 using, 37–38
Index 253

Empirical models, xxii Flash equation, 146–147

Energy balance equation Flashing, 119
Bernoulli’s equation, 77–78 Flow arrangement, 107
general, 75–76 Flow diagram, types, 191
mechanical, 76 Flow sheeting, 191
pressure drop and friction losses, 78–79 Flow work, 76
Energy balance, role of, 22 Fluid dynamics, xxv, 70
Energy content of fuels, 246 Fluid flow, 20
Energy conversion, gas volume to, 245 classification of, 71–72
Energy units and conversions, 245 in pipes, 83
Engineering aspect of chemical process, 48 Fluid mechanics, definitions and
Engineering science, xxv terminology in, 70–71
Entropy, 179–180 Fluids
solved examples, 181–182 defined, 69
Equations of state, 178–179 nature of, 71
Equilibrium constant, for chemical reaction, 24 Fluid statics, 70
Equilibrium problems, 47, 241 gauge pressure and absolute pressure,
Equilibrium stage, 122, 140 74–75
Equilibrium state, 178 Forced convection, natural convection vs., 101
Ethanol–water system, Txy diagram for, 59 Forces, types of, 70
Excel Formulating mathematical modeling, 47–49
BP temperature calculation, 53 Fossil fuels, CO2 pollution of, 246
flow direction, determination, 90–91 Fourier’s law, 96–98
McCabe–Thiele method, problem solving by, Fractional distillation, see Distillation
134–135 Free energy of formation of reaction, 180–181
plate-to-plate calculations by, 137 Free stream velocity, 74
problem solving using, 37, 46 Friction losses, pressure drop and, 78–79
shell and tube heat exchanger, calculation, Fuels, energy content of, 246
112–113
solution of linear equation system, 40–41 G
Txy diagram for benzene–toluene mixture
using, 60–62, 64 Gas constant, 10
values of, 236
F Gas laws
Amagat’s law, 13
Fahrenheit temperature scale, 6 Avogadro’s hypothesis, 14
False position (FP) method, 129 Boyle’s law, 9
FCI, see Fixed capital investment Charles’ law, 9
Fenske equation, 142 Dalton’s law, 9–10
Fenske–Underwood–Gilliland, see Shortcut ideal gas law, 10–12
calculation methods Raoult’s law, 12–13
Fertile water, 210 Gas volume to energy conversion, 245
Finite-stage contactors, 123 Gauge pressure, and absolute pressure, 74–75
Fire pumps, 85 General energy balance equation, 75–76
First law of thermodynamics, 26, 179 Gilliland method, 142, 143
First-order reaction, 169, 170 Gravity force, 70
Fixed-bed reactor, 176 Gray box models, see Semiempirical models
Fixed capital investment (FCI), 193–194
Flash dewatering of raw sewage effluents H
(case study)
conclusions, 207 Heat balance (HB), 25, 188
discussions, 208 Heat exchangers
process description, 206–207 design, 109–110
proposed scheme, 204, 206 example, 110
Flash distillation, 50, 144–145 LMTD, 108–109
example, 58–59 shell and tube, 109
problem, 24, 25 types, 107–108
254 Index

Heat flow, 95 Lithium hydroxide, 31

Heat transfer Log mean temperature difference (LMTD),
coefficient, calculating, 14 108–109
by conduction (see Conduction, heat calculating, 110
transfer by)
by convection, 101–103 M
modes of, 96–97
by radiation, 106–107 Magnesium chloride, 210
temperature and heat flow, 95 Magnesium extraction from seawater
Henry’s law, 13 (case study), 208–210
Heterogeneous catalysis reactor types, 175 Magnesium metal, production of, 210
High-pressure pumps, 85 Marine pumps, 85
Hollow cylinder, conduction through, 99 Mass and energy conservation, 25
Homemade soap, 216 Mass transfer, xxv, 96, 122, 138
Horsepower (HP) for pump Material balance (MB)
calculation, 86 calculations, 25, 151, 188
solved examples, 89 in process design, 190
role, 22
I Mathematical constant, 235–236
Mathematical formula, principles to, 24–25
Ideal fluid flow, 72 Mathematical modeling, 241
Ideal gas constant, see Gas constant formulating, 47–49
Ideal gas law, 10–12 MATLAB®
Industrial catalytic reactors, 173 chemical equilibrium inside chemical
Industrial production of CO2, 29 reactor, 184
Industrial pumps, 85 derivative function, calculating, 39
Integrated rate law, 165, 170–172 distillation column, 158
Integration, example, 38–39 heat transfer rate, calculations by, 100
Internal-flow convection correlations, 116–117 linear equation system using, 54–55, 111
International System of Units, 3–5 problem solving, 37, 46
Interphase operations, 119, 120 Matrix, solution using, 39, 42–43
Intraphase separation, 121 McCabe–Thiele method
Irrotational flow, see Ideal fluid flow assumptions, 132
plate-to-plate calculations, 135–137
K problem solving by using Excel, 134–135
procedure, 132–134
Kelvin temperature scale, 6 stage design and efficiency, 140–141
Kettle-type reboiler, 127 total and minimum reflux, 138
Kinematic viscosity, 71 tray efficiency, 138–140
Kinetic energy Mean residence time, 176–177
of flowing water, 15 Mechanical energy balance, 76
of missile, 30 Methanol in reactor, per pass conversion of,
Kremser equations, 155 182–183
Methyl acetate, production of, 218, 219
L Minimum number of stages, 129
Minimum reflux (MR), 129, 138
Laboratory catalytic reactors, types, 173 Mixed flow pumps, 85
Laminar flow Modern chemical engineering, xxiii
friction factor, 79 Molar constant, see Gas constant
parameters, 73–74 Molar mass, 11
Linear equation system Momentum, heat, and mass (MHM), xxiv
Excel, solution by, 40–41 Moody chart, 79
MATLAB®, solution using, 54–55 MSFE, see Multistage flash evaporation
numerical solution of, 36 Mud pumps, 85
Linear programming problem, 37 Multistage flash evaporation (MSFE),
Liquid–gas mass transfer operations, 119 204, 206,  208
Liquid product, 127 Murphree efficiency, 139
Index 255

N Payout period, 196

Petrochemical pumps, 85
Natural convection vs. forced convection, 101 Petroleum fractionation process,
Natural gas field processing, absorption role xxiii–xxv
in, 156–157 Physical changes, see Physical separation
Nature of fluids, 71 Physical events, conversion of,
Nernst equation, 10 24–25
Net present value (NPV), 196 Physical models for distillation, 131
example, 200 Physical operations, xxiii
Newtonian fluid, 71 Physical separation, 20
Newton–Raphson method, 240 process, 30
example, 38 Physicochemical changes, 21, 188
Newton’s law of viscosity, xxvi–xxvii Pinch point, 138
Newton’s method, BP temperature calculation Pipe diameter and pressure drops,
by, 52–53 82–83
Newton’s second law, 70–71 Pipeline capacity, 83
Noncompressible fluid, 70 Piping
Nonlinear equations, numerical solution of economic balance in, 80–81
systems of, 36–37 pipe diameter and pressure drops,
Nonnewtonian fluid, 71 82–83
Nonuniform flow, 72 sizing, 23–24, 80
Normal stress, 70 wall thickness, procedure to calculate,
Number of trays, calculation of, 131 81–82
Numerical methods Plant design, see Chemical plant, design of
applications using elementary, 37–38 Plate-to-plate calculations
areas and domain of, 36–37 rectification column, 135–137
development, 35 stripping column, 137
formulation of mathematical model Pneumatic pumps, 85
through, 49 Polonium, radioactive decay of, 42
Numerical root-finding methods, Potential flow, see Ideal fluid flow
237–240 Power conversion, 245
Practical component, xxii
O Prandtl numbers, 116
Preferential salt separation (PSS), 209
One-dimensional steady-state heat conduction, Present value index (PVI), 196
97, 98 Pressure, 70
Operating pressure Pressure drop
effect of, 127–128 and friction losses, 78–79
solved example, 128–129 pipe diameter and, 82–83
Optimum economic pipe diameter, Pressure force, 70
80–81 Pressure pumps, 85
Ordinary differential equations, 216 Pressure scale, 7, 9
Overall efficiency, 139 Problem solving using computers,
Overall heat transfer coefficient, 46–47
103–105 Process design, 22
example, 105–106 Process equipment, 23–24
Overhead condensers, 125–126 Process pumps, 85
Overhead product, 124, 127 Process variables
pressure scale, 7, 9
P temperature scales, 6–8
Product formation reaction, 212
Parallel flow, 107, 108 Profitability analysis using economic
Partial condenser, 125–126 indicators
Partial reboilers, 127 annual rate of return, 195
Parts-per notation, 26 DCFR and PVI, 196
Pascal, 7 NPV, 196
Payback time, see Payout period payout period, 196
256 Index

Programming languages, 36 Scientific problems, solving, xxii

Propagation problems, 47, 241 Secant method, 240
Pumps Second law of thermodynamics, 26, 179
classification and types of, 84 Second-order reaction, 169, 170
fluid flow, 83 Semiempirical models, xxii
horsepower, calculation of, 86 Separation factor (SF), 122
powerful, 80 Sewage treatment process, 205
selection, 85–86 Shear force, 70
Pxy diagram of acetonitrile, 64–65 Shear stress, 70, 74
Shell and tube heat exchanger, 109
Q solved example, 112–113
Shortcut calculation methods
Quantitative process, 48 column diameter, 144
Fenske equation, 142
R Gilliland method, 142, 143
Underwood equation, 142–143
Radiation, heat transfer by, 97, 106–107 Single displacement reaction, 167
Radioactive decay of polonium, 42 Single-stage contact unit, 140
Raoult’s law, 12–13, 50, 55, 63 Sinking-fund factor (SFF), 194
Rate constant, 169 Slurry pumps, 85
Rate law, forms of Soap, 216
differential rate law, 165, 168–170 Sodium chloride, 216, 217
integrated rate law, 170–172 Sodium sulfite, 27–28
Rate of shear stress, 73–74 Solar hydrogen, to desert development using
Rating (operational) problem, in distillation, ammonia, 202
130–131 Solar pumps, 86
Reaction kinetics, 166 Solids in series, conduction through, 99
chemical reactions, categories of, Solvay process, 210
167–168 proposed process and, 213
reaction rates (see Reaction rates) Solved examples
role, 27 absolute pressure, 18
Reaction rates absorption, 152–154
differential rate law, 165, 168–170 acetonitrile, Pxy diagram of, 64–65
integrated rate law, 170–172 acetylene and hydrogen, yield of, 184–186
Reactive distillation, 147 acid concentration, finding, 41–42
case study, 218–219 algorithm, 38
Real fluid, 71 annual depreciation costs, 198–199
flow, 72 bed temperature, estimation, 113–116
Reboilers, 127 benzene, 31–32
Rectification, 119 benzene–toluene mixture, Txy diagram for,
in distillation columns, 127, 130 60–62, 64
Reflux, 126–127 Bernoulli’s equation, 87, 88
Reflux ratio, 126–127, 129, 139 BP temperature calculation, 52–53, 55–56
Reforming unit, xxiv chemical equilibrium inside chemical
Relative volatility, 121 reactors, using MATLAB®, 184
Reynolds (Re) number, 79, 116, 117 combustion of heptane, 30
Root-finding methods, 236 composition of streams, calculation,
analytical solution, 237 159–160
numerical, 237–240 conduction, heat transfer by, 99–101
Rule-of-thumb economic velocity, 83 DCFR, 199–200
dew-pressure calculation, 54, 56–57
S diameter column, 163–164
differentiation, 39
Safety factors in plant design, 191, 192 distillation column, 58, 157
Saponification process, 216, 217 entropy, calculations, 181–182
Scientific point of view, 48 ethanol–water system, Txy diagram for, 59
Index 257

flash distillation (separation), 58–59 Synthesis process, 212, 241

flow direction, determination, 89–91 Synthesis reaction, 167
flow rates for product streams, 196–197 Systems of units, 3–5
heat transfer coefficient, 14
horsepower for pump, calculation, 89 T
industrial production of CO2, 29
integration, 38–39 Tangential stress, 70
kinetic energy, 15, 30 Tangent method, see Newton–Raphson method
linear equation system by Excel, 40–41 Temperature, 95
linear equation system by MATLAB®, 54–55 scales, 6–8
lithium hydroxide, calculation, 31 Terminal velocity of spherical particle, solved
mass flow rates of outlet stream, calculation, examples, 91–92
160–161, 197–198 Theoretical approach, xxii
matrix method, 39, 42–43 Theoretical component, xxii
methane gas, molar volume and density, 17 Theoretical models, xxii
methanol in reactor, per pass conversion of, Theoretical stage, see Equilibrium stage
182–183 Thermal conductivity, 96–98
minimum reflux ratio, 163–164 Thermal decomposition of NO2, 23
Newton–Raphson method, 38 Thermal radiation, 97, 106
NPV, 200 Thermodynamics
operating pressure, 128–129 defined, 165
partial differential equation, 110–111 entropy, 179–180
physical properties for water, equations of state, 178–179
estimation, 116 equilibrium concept, 178
physical separation process, 30 free energy of formation of reaction,
pipeline diameter, calculating, 89 180–181
product component flow rates, calculation, laws, 26, 179
184–186 process concept, 178
radioactive decay of polonium, 42 role of, 22–23, 27
Raoult’s law, 55, 63 Third law of thermodynamics, 26, 179
shell and tube heat exchanger, 112–113 Time-varying problems, 47, 241
sodium sulfite, 27–28 Total capital investment, 193–194
solvent recovery system, 31–32 Total condenser, 125
terminal velocity of spherical particle, Total head, 78
91–92 Total reflux (TR), 138
thermodynamic feasibility of chemical Transfer unit concept for absorption, 156
reaction, 182 Transient problems, 47, 241
thickener, area and diameter of, 92–94 Transparent models, see Theoretical models
total pressure, calculating, 15 Transport phenomena, xxiii
Txy diagram for ethanol–water system, 59 role of, xxv–xxvii
van der Waals equation, 16 Tray efficiency, 138–140
vapor-liquid-equilibrium (VLE) data, 63 Trial and error procedures, 37
water–ethanol mixture, average density of, 43 Turbulent flow, 72
S200 Omni Processor, 207 Txy diagram
Space time, 177–178 for benzene–toluene mixture using Excel,
Standard atmosphere, 7 60–62, 64
Static pressure, 74 for ethanol–water system, 59
Steady state flow, 72
Stoke, 71 U
Stress, defined, 69–70
Stripping Underwood equation, 142–143
analytical methods, 154–156 Uniform flow, 72
defined, 119, 147 Unit operations, xxiv, 19–20
design, 149 role of, xxv–xxvii
in distillation columns, 127, 130 Unit process, xxiv, 20
operating line and equilibrium curve for, 150 role of, xxv–xxvii
258 Index

Universal constant, see Gas constant Velocity gradient, 73–74

Unsteady state flow, 72 Viscosity, 71
U-type heat exchanger, 108
W
V
Water pumps, 86
Values of gas constants, 236 Well pumps, 86
van der Waals equation, 11
example, 16 Z
Vapor–liquid equilibrium constant, 147
Vapor pressure, 121 Zero-order reaction, 169, 170
Vapor product, 127 Zeroth law of thermodynamics, 26, 179